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ASPHALTS 

AND 

ALLIED    SUBSTANCES 

Their  Occurrence,  Modes  of  Production, 
Uses  in  the  dirts  and  Methods  of  Testing 

BY 
HERBERT  ABRAHAM 

President^  The  Rnberoid  Co.;    President ',  Asphalt  Shingle  and 

Roofing  Industry 


FOURTH  EDITION 


NEW  YORK 

D.  VAN  NOSTRAND  COMPANY,  INC. 

250   FOURTH   AVENUE 


Copyright,  1918  and  1920, 

BY 
D.  VAN  NOSTRAND   COMPANY 


Copyright,  1929,  1938  by 
D.  VAN  NOSTRAND   COMPANY,  INC. 


All  rights  reserved.  No  part  of  this  book  may 
be  reproduced  in  any  form  without  permission 
in  writing  from  the  publisher,  except  by  a 
reviewer  who  may  quote  brief  passages  in  a 
review  to  be  printed  in  a  magazine  or  newspaper. 


First  Published,  August  1918 


Second  Edition,  August  1920 


Third  Edition,  November  1929 

Reprinted,  April  1932 


Fourth  Edition,  January  1938 


PRINTED  IN   U.  3.  A. 


PRESS    OF 

BRAUNWORTH    &    CO..    INC. 
BUILDERS    OF    BOOKS 
BRIDGEPORT.   CONN. 


PREFACE  TO  FOURTH  EDITION 

The  present  edition  of  "Asphalts  and  Allied  Substances"  has 
been  revised  in  several  material  respects.  Although  in  the  main, 
the  textual  sequence  of  the  earlier  editions  has  been  followed,  the 
subject  matter  has  been  amplified  so  as  to  cover  the  ground  more 
intensively  from  the  earliest  dawn  of  civilization,  down  to  the  very 
last  word  in  this  rapidly  growing  branch  of  technology. 

Several  new  chapters  have  been  added.  The  section  relating  to 
"Methods  of  Testing"  has  been  completely  rewritten  to  conform 
with  the  most  recent  practices.  References  to  patents  and  to  the  gen- 
eral literature  have  been  brought  up  to  date,  and  more  than  12,000 
such  citations  have  been  segregated  in  an  appendix  at  the  end  of  the 
volume,  where  they  would  not  interfere  with  the  continuity  of  the 
text  and  yet  be  readily  accessible  to  the  interested  reader.  The  "Bib- 
liography" has  likewise  been  expanded  to  embrace  more  than  900 
treatises. 

No  effort  has  been  spared  to  make  this  new  edition  as  compre- 
hensive as  the  limitations  of  space  and  the  author's  available  time 
have  permitted. 

HERBERT  ABRAHAM. 

NEW  YORK  CITY, 

September  15,  1937. 


PREFACE  TO  THIRD  EDITION 

During  the  decade  which  has  elapsed  since  the  publication  of  the 
Second  Edition  of  <4Asphalts  and  Allied  Substances/'  the  technology 
of  bituminous  substances  has  made  great  strides  under  the  pressure 
of  rapidly  increasing  production.  The  output  of  crude  petroleum 
has  not  only  increased- by  leaps  and  bounds,  but  has  gravitated  to- 
wards oil-fields  yielding  a  greater  percentage  output  of  asphalt.  Sim- 
ilarly, coal  tar  and  coal-tar  pitch  have  been  produced  in  larger 
amounts,  because  of  the  widespread  introduction  of  equipment  for 
recovering  these  valuable  by-products. 

Accordingly,  the  supply  of  petroleum  asphalt  and  coal-tar  resid- 
uals has  more  than  kept  pace  with  their  utilization  in  the  arts,  and 
this  has  been  reflected  by  a  substantial  reduction  in  their  market 
price.  Not  only  has  this  condition  rendered  these  substances  avail- 
able to  a  larger  consuming  field,  but  it  has  also  served  to  stimulate 
inventors  to  adapt  them  to  new  uses. 

The  increasing  commercial  importance  of  bituminous  substances 
has  been  evidenced  by  greater  efforts  to  perfect  and  standardize 
their  methods  of  test,  through  such  agencies  as  The  Federal  Speci- 
fication Board  (organized  by  the  United  States  Government),  and 
many  scientific  societies,  including  especially  the  American  Society 
for  Testing  Materials,  through  wrhose  courtesy  the  author  has  been 
given  permission  to  reprint  their  specifications  and  tests  in  this  book. 

To  keep  pace  with  this  rapidly  developing  art,  it  has  accordingly 
been  necessary  to  rewrite  the  book  completely,  and  thereby  bring  it 
up-to-date. 

HERBERT  ABRAHAM 

NEW  YORK  Cn% 
November  i,  1929* 


vii 


PREFACE  TO  FIRST  EDITION 

This  treatise  has  been  written  for  those  interested  in  the  fabrica- 
tion, merchandising  and  application  of  bituminous  products.  It 
embraces:  (i)  methods  serving  as  a  guide  for  the  works  chemist 
engaged  in  testing  and  analyzing  raw  and  manufactured  products; 
(2 )  data  for  assisting  the  refinery  or  factory  superintendent  in  blend- 
ing and  compounding  mixtures;  (3)  information  enabling  the  am- 
bitious salesman  to  enlarge  his  knowledge  concerning  the  scope  and 
limitations  of  the  articles  he  vends;  and  (4)  the  principles  underly- 
ing the  practical  application  of  bituminous  products  for  structural 
purposes,  of  interest  to  the  engineer,  contractor  and  architect.  Sub- 
ject-matter of  sole  value  to  the  technical  man  has  been  segregated  in 
Part  V,  uMethods  of  Testing,"  excepting  the  outline  of  the  "Chem- 
istry of  Bituminous  Substances"  appearing  in  Chapter  III.  These 
sections,  however,  may  be  passed  over  by  the  non-technical  man, 
without  interfering  materially  with  the  continuity  of  the  work. 

In  view  of  the  vast  amount  of  ground  covered  in  this  volume,  and 
fully  realizing  the  limitations  of  his  proficiency  in  some  of  its 
branches  and  ramifications,  the  author  has  taken  it  upon  himself  to 
draw  freely  from  contemporary  text-books  and  journal  articles.  In 
such  instances,  his  endeavor  has  been  to  place  due  credit  where  it 
belongs,  by  referring  to  the  source  of  such  extraneous  information. 
Nevertheless,  there  has  been  included  a  substantial  amount  of  orig- 
inal data  accumulated  by  the  author  during  the  past  nineteen  years, 
most  of  which  appears  in  print  herein  for  the  first  time. 

Topics  which  have  been  ably  presented  in  other  reference  books, 
as  for  example  the  technology  of  pavements,  etc.,  have  purposely 
been  subordinated  to  those  concerning  which  little  data  have  hitherto 
been  available.  To  the  latter  belong  such  subjects  as  petroleum 
asphalts ;  fatty-acid  pitches ;  bituminized  roofings,  floorings  and  other 
fabrics;  bituminous  paints,  cements,  varnishes  and  japans. 

Certain  branches  of  the  industry  have  developed  along  different 
lines  in  Europe  than  has  been  the  case  in  this  country,  especially 


IX 


X  PREFACE  TO  FIRST  EDITION 

the  treatment  of  peat  and  lignite  (Chapter  XV),  also  pyrobitumin- 
ous  shales  (Chapter  XVI) .  In  such  instances,  the  methods  in  vogue 
abroad  before  the  great  war  are  described  with  more  or  less  detail. 
It  must  be  borne  in  mind  in  this  connection,  that  the  war  has  mate- 
rially interfered  with  the  prosecution  of  these  industries  abroad,  and 
the  data  presented  should  be  so  construed,  even  though  not  specific- 
ally stated  in  the  text. 

Whereas  the  greatest  pains  have  been  taken  to  establish  the  ac- 
curacy of  every  assertion,  as  well  as  the  authenticity  of  every  alleged 
fact,  the  author  does  not  flatter  himself  that  he  has  escaped  the 
pitfalls  which  must  perforce  beset  the  path  of  a  writer  who  under- 
takes to  delve  into  a  subject  as  complicated  as  the  one  under  consid- 
eration, concerning  which  there  are  so  many  divergent  views. 

Appreciation  is  expressed  for  the  valuable  suggestions  and  assist- 
ance rendered  by  W.  A.  Hamor,  D.  R.  Steuart,  Prevost  Hubbard, 
S.  R.  Church,  E.  B.  Cobb,  David  Wesson,  Clifford  Richardson,  S.  C. 
Ells,  and  the  author's  immediate  associates. 

HERBERT  ABRAHAM. 

NEW  YORK  CITY, 
July  i,  1918. 


TABLE  OF  CONTENTS 


PART  I— GENERAL  CONSIDERATIONS 
CHAPTER  I 

PAGE 

HISTORICAL  REVIEW  x 

Origin  of  the  Words  "Asphalt,"  "Bitumen"  and  "Pitch"— Fossils  Preserved 
by  Means  of  Asphalt — Use  of  Asphalt  by  the  Sumerians  (about  3800  to  2500 
B.C.) — King  Sargon  of  Accad  (about  3800  B.C.) — Manishtusu  King  of  Kish 
(about  3600  B.C.) — Ornaments  (about  3500  B.C.) — At  Tell-Asmar  in  Eshunna 
(3200  to  2900  B.C.) — Lugal-daudu  King  of  A  dab  (about  3000  B.C.) — Ente- 
mena  of  Shirpula  (about  2850  B.C.) — Ur-Nind  King  of  Lagash  (about  2800 
B.C.) — Ornaments  and  Sculptured  Objects  (2800  to  2500  B.C.) — Gudea  of 
Lagash  (about  2700  B.C.) — Tablets  of  Gilgamish  (about  2500  B.C.) — Bur- 
Sin  King  of  Ur  (about  2500  B.C.) — Use  of  Asphalt  by  Pre-historic  Races 
in  India  (about  3000  B.C.) — Use  of  Asphalt  by  the  Early  Egyptians  (2500 
to  1500  B.C.) — Use  of  Asphalt  in  Biblical  Times  (2500  to  1500  B.C.) — Use 
of  Asphalt  by  the  Babylonians  (2500  to  538  B.C.) — King  Khammurabi  (about 
2200  B.C.) — Queen  S  emir  amis  (about  700  B.C.) — King  Nabopolassar  (625  to 
604  B.C.) — King  Nebuchadnezzar  (604  to  561  B.C.) — Use  of  Asphalt  by  the 
Assyrians  (1400  to  607  B.C.) — King  Adad-Nirari  1  (about  1300  B.C.) — King 
Tukulti-Ninurta  II  (890  to  884  B.C.) — King  Sargon  (722  to  705  B.C.) — 
King  Sennacherib  (704  to  682  B.C.) — Use  of  Asphalt  in  Constructing  Lake- 
Dwellings  (about  1000  B.C.) — References  to  Bituminous  Substances  by  Greek 
and  Roman  Writers  (500  B.C.  to  817  A.D.) — Herodotus  (484-425  B.C.) — 
Thucydides  (471-401  B.C.) — Hippocrates  (460-377  B.C.) — Xenophon  (430- 
357  B.C.) — Aristotle  (384-322  B.C.) — Theophrastus  (372-288  B.C.) — Antigonus 
(about  311  B.C.) — Hannibal  (247-183  B.C.) — Vergil  (70-19  B.C.) — Strabo 
63  B.C. — 24  A.D.) — Diodorus  Siculus  (about  50  A.D.) — Virtuvius  (about  50 
A.D.) — Pliny  the  Elder  (23-79  A.D.) — Josephus  Flavius  (37-95  A.D.) — Plutarch 
(about  46  A.D.) — Tacitus  (55-117  A.D.) — Aelian  (Aelianus  Claudius)  (about 
loo  A.D.) — Dioscorides  (about  150  A.D.) — Dion  Cassius  (155-230  A.D.) — 
Philostratus  (The  Elder)  (about  200  A.D.) — Geoponica  (200-300  A.D.) — Afri- 
canus  (about  300  A.D.) — Ammianus  Marcellinus  (330-395  A.D.) — Theophanes 
(758-817  A.D.) — About  950  A.D.,  Abu-L-Hasan  Masudi — About  985  A.D.,  Abd 
Al  Mukaddasi — About  1248  AJX,  Pierre  de  Joinville — About  1300  A.D.  Marco 
Polo— About  1350  A.D.,  Sir  John-  Mandeville — 1494-1555,  Georg  Agricola — 
1498,  Christopher  Columbus — About  1500,  Use  of  Asphalt  in  Peru — 1535, 
Discovery  of  Asphalt  in  Cuba — 1563,  Cesar  Fredericke — 1595,  Sir  Walter 
Raleigh-— 1599,  First  Classification  of  Bituminous  Substance*— 1608,  William 
Shakespeare—i 6 5 6,  Early  Dictionary  Definition  of  "Bitumen" — 1660,  John 
Milton — 1661,  Commercial  Production  of  Wood  Tar — 1672,  First  Accurate 
Description  of  Persian  Asphalt  Deposits— 1673,  Discovery  of  Elaterite— 1681, 

xi 


xii  TABLE  OF  CONTENTS 

PAGE 

Discovery  of  Coal  Tar  and  Coal-Tar  Pitch — 1691,  Discovery  of  Illuminating 
Gas  from  Coal — 1694,  Discovery  of  Shale  Tar  and  Shale-tar  Pitch — 1712- 
1730,  Discovery  of  Val  de  Travers,  Limmer  and  Seyssel  Asphalt  Deposits — 
1722,  First  Use  of  Tar  for  Flat  Roofs — 1746,  Invention  of  the  Process  of 
Refining  Coal  Tar — 1752,  Samuel  Foote — 1777,  First  Exposition  of  Modern 
Theory  of  the  Origin  of  Asphalt — 1788,  Discovery  of  Lignite  Tar — 1780- 
1790,  Discovery  of  "Composition"  or  "Prepared"  Roofing — 1792-1802,  Manu- 
facture of  Coal  Gas  and  Coal  Tar  on  a  Large  Scale — 1797-1802,  Exploitation 
of  Seyssel  Asphalt  in  France — 1815,  Commercial  Exploitation  of  Coal-tar 
Solvents — 1820,  Manufacture  of  Asphalt-saturated  Packing  Papers  in  Switzer- 
land— 1822,  Discovery  of  Scheereite  and  Hatchettite — 1830,  Discovery  of 
Paraffin  Wax — 1832,  Coal-tar  First  Used  for  Paving — 1833,  Discovery  of 
Ozokerite — 1835,  First  Asphalt  Mastic  Foot  Pavements  Laid  in  Paris — 1836, 
Asphalt  First  Used  in  London  for  Foot  Pavements — 1837,  Publication  of  First 
Exhaustive  Treatise  on  the  Chemistry  of  Asphalt — 1837,  Discovery  of  Bitu- 
minous Matter  in  the  United  States — 1838,  Discovery  of  Process  for  Preserv- 
ing Wood  with  Coal-tar  Creosote — 1838,  Asphalt  First  Used  in  the  United 
States  for  Foot  Pavements — 1841,  First  Use  of  Wood  Block  Pavement — 1843, 
Bituminous  Matters  Discovered  in  New  York  State — 1844-1847,  First  Compo- 
sition Roofing  in  the  United  States — 1850,  Discovery  of  "Asphaltic  Coal"  in 
New  Brunswick,  Nova  Scotia — 1852,  First  Modern  Asphaltic  Road — 1854, 
First  Compressed  Asphalt  Roadway  Laid  in  Paris — 1858,  First  Modern  As- 
phalt Pavement  Laid  in  Paris — 1863,  Discovery  of  Grahamite  in  West  Vir- 
ginia— 1869,  The  First  Compressed  Asphalt  Pavement  in  London — 1870-1873, 
First  Asphalt  Roadways  in  the  United  States — 1876,  First  Trinidad  Asphalt 
Pavement  Laid  in  the  United  States — 1880,  Use  of  Asphalt  "Chewing-gum" 
in  Mexico — 1881,  Use  of  Chemicals  for  Oxidizing  Coal  Tars  and  Petroleum 
Asphalts — 1885,  Discovery  of  Uintaite  (Gilsonite)  in  Utah — 1889,  Discovery 
of  Wurtzilite  in  Utah — 1891,  Exploitation  of  the  Bermudez  Asphalt  Deposit, 
Venezuela — 1892,  Use  of  Bermudez  Asphalt  on  a  Large  Scale — 1894,  Use  °f 
Air  for  Oxidizing  Petroleum  Asphalt 

CHAPTER  II 

TERMINOLOGY  AND  CLASSIFICATION  OF  BITUMINOUS  SUBSTANCES      51 

Bituminous  Substances — Bitumen — Pyrobitumen — Petroleum — Mineral  Wax — 
Asphalt — Asphaltite — Asphaltic  Pyrobitumen — Non-asphaltic  Pyrobitumen — 
Tar — Pitch — Classification  of  Bituminous  Substances. 


CHAPTER  III 

CHEMISTRY  OF  BITUMINOUS   SUBSTANCES 65 

Composition  of  Non-mineral  Matrix — Composition  of  Associated  Min- 
eral Constituents — Composition  of  Associated  Non-mineral  Constitu- 
ents— Behavior  with  Solvents — Behavior  on  Subjecting  to  Heat — Re- 
actions with  Gases  —  Oxygenation  —  Hydrogenation  —  Reactions  with 
Acids — Liquid  Sulfur  Dioxide — Sulfuric  Acid  and  Sulfur  Trioxide — Nitric 
Acid — Sulfuric  Acid  and  Formaldehyde — Reactions  with  Alkalies — Reac- 
tions with  Metalloids — Sulfur  and  Sulfur  Dichloride — Selenium — Phos- 
phorus—Halogens— Reactions  with  Metallic  Salts. 


TABLE  OF  CONTENTS  xiii 

CHAPTER  IV 

PAGE 

GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND  PYROBITUMENS 82 

Geology — Age  of  the  Geological  Formations — Character  of  the  Associated 
Minerals — Modes  of  Occurrence — Springs — Lakes — Seepages — Subterranean 
Pools  or  Reservoirs — Impregnated  Rock  in  Strata — Filling  Veins — Movement 
of  Bitumen  in  the  Earth's  Strata — Hydrostatic  Pressure — Gas  Pressure — 
Capillarity — Gravitation — Effect  of  Heat — Origin  and  Metamorphosis  of 
Bitumens  and  Asphaltic  Pyrobitumens — Probable  Origin  of  Bitumens 
and  Asphaltic  Pyrobitumens — Inorganic  Theories — Vegetable  Theories — Ani- 
mal Theories — Metamorphosis  of  Mineral  Waxes,  Asphalts,  Asphaltites  and 
Asphallic-Pyrobitumens  from  Petroleum — Origin  and  Metamorphosis  of 
Non-Asphaltic  Pyrobitumens. 

CHAPTER  V 

ANNUAL  PRODUCTION   OF  BITUMINOUS  SUBSTANCES   AND   THEIR 

MANUFACTURED    PRODUCTS    98 

Production  of  Asphalts,  Asphaltites  and  Asphaltic  Pyrobitumens — 
World  Production — Production  in  the  United  States — Production  of  Tars 
and  Pitches — Tars  Derived  from  Coal — Tars  and  Pitches  Derived  from 
Wood — Other  Tars  and  Pitches — Manufactured  Products — Bituminous 
Paving  Materials — Bituminous  Roofing  Products — Asphalted  Felt-base  Floor 
Coverings. 


PART  II— SEMI-SOLID  AND  SOLID  BITUMENS  AND 

PYROBITUMENS 

CHAPTER  VI 

METHODS  OF  MINING,  TRANSPORTING  AND  REFINING 112 

Mining  Methods — Open-cut  Quarrying — Tunnelling — Special  Methods — 
Methods  of  Shipment  and  Transportation — Methods  of  Refining — De- 
hydration —  Distillation  —  Comminution  —  Sedimentation  —  Extraction 
— Extraction  by  Means  of  Water — Extraction  or  Precipitation  with  Solvents — 
Methods  of  Storage. 

CHAPTER  VII 

MINERAL  WAXES   129 

Ozokerite— Europe — Galicia — Rumania — Russia — Terek  Province — Kuban 
Province — Kutais  Province — Tiflis  Province — Baku  Province — Kars  Province 
— Asia — State  of  Turkestan — Siberia — Philippine  Islands — North  America 
—United  States— Utafi—Texas—Hatchettite  or  Hatchettine— Scheereite 
Kabaite — Montan  Wax. 


Xiv  TABLE  OF  CONTENTS 

CHAPTER  VIII 

PAGE 

NATIVE  ASPHALTS  OCCURRING  IN  A  FAIRLY  PURE  STATE 139 

North  America — United  States — Kentucky — Oklahoma — Utah — California — 
Oregon — Mexico — State  of  Tamaulipas — State  of  Vera  Cruz — Cuba — Prov- 
ince of  Matanzas — Province  of  Santa  Clara — Province  of  Camaguey — Province 
of  Santiago  de  Cuba — South  America — Venezuela — State  of  Bermudez — State 
of  Zulia — Europe — France — Department  of  Puy  de  Dome — Albania — Se*le- 
nitza  —  Greece  —  Zante  —  Russia — Kutais  Province — Tiflis  Province — Uralsk 
Province — Asia — Syria — Villayet  of  Beirut — Mesopotamia  (Iraq) — Hit — Ain 
el  Maraj — Ain  Ma*  Moura — Quijarah,  Ramadi  and  Abu  Gir — Asiatic  Russia 
— Sakhalin — Philippine  Islands — Island  of  Leyte. 

CHAPTER  IX 

NATIVE  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 155 

North  America — United  States — Kentucky — Missouri — Indiana — Oklahoma — 
Arkansas  —  Alabama  —  Louisiana  —  Texas  —  Utah  —  Wyoming  —  Cali- 
fornia— Canada — Alberta  Province — Manitoba  Province — Mexico — States  of 
Vera  Cruz  and  Tamaulipas — Cuba — Province  of  Matanzas — Province  of  Pinar 
del  Rio — Province  of  Havana — Province  of  Camaguey — Province  of  Santiago 
de  Cuba — South  America — Trinidad — Brazil — State  of  Parand — State  of 
Sao  Paulo — Argentina — Province  of  Jujuy — Province  of  Chubut — Province 
of  Mendoza — Colombia — Department  of  Bolivar — Department  of  Antioquia — 
Department  of  Santander — Department  of  Boyacd — Equador — Province  of 
Guayas — Europe — France — Department  of  Landes — Department  of  Gard — 
Department  of  Haute-Savoie — Department  of  Ain — Department  of  Basses- 
Alpes — Department  of  Puy~de-D6me — Department  of  Haute  Vienne — Switzer- 
land —  Alsace-Lorraine  —  Spain  —  Burgos  Province  —  Germany — Province  of 
Hanover — Province  of  Westphalia — Province  of  Hessen — Province  of  Baden 
— Province  of  Silesia — Jugoslavia — Province  of  Dalmatia — Province  of  Herze- 
govina— Province  of  Styria — Austria — Province  of  Tyrol — Hungary — Prov- 
ince of  Bihar — Czecho-Slo<vakia — Province  of  Trencsen — Provinces  of  Moravia 
and  Silesia — Rumania — Albania — S61enitza — Italy — Compartment  of  Marches 
— Compartment  of  Abruzzi  e  Molise — Compartment  of  Calabria — Compart- 
ment of  Campania — Compartment  of  Sicily — Greece — Department  of  Triphylia 
— Department  of  Achaia — lolian  Islands — Department  of  Phocis — Depart- 
ment of  Phthiotis — Departments  of  Eurytania  and  Arta — Northern  Depart- 
ments— Portugal — Province  of  Estremadura — Spain — Province  of  Santander — 
Province  of  Alava — Province  of  Navarre — Province  of  Gerona — Province  of 
Tarragona — Province  of  Soria — Province  of  Burgos — Province  of  Almeria — 
Province  of  Valencia — Russia  (in  Europe) — Simbirsk  Province — Kazan  Prov- 
ince— Samara  Province — Terek  Province — Kutais  Province — Tiflis  Province — 
Baku  Province— Asia— Syria  (Levant  States)  —Vilayet  of  Aleppo—Vilayet  of 
Beirut— Vilayet  of  Sham— Palestine-— Mesopotamia  (Iraq)—  Valiyet  of  Bagdad 
—Asiatic  Russia—  Uralsk  Province— State  of  Turkestan— Kamchatka  Penin- 
sula—Sakhalin Island—  Tur key-in- Asia  (Asia  Minor)— Anatolia— Arabi a— 
Vilayet  of  El  Hasa— Sinai  Peninsula— -Egypt— India— Kashmir  District— Ha- 
zara  District— Bel uchistan  District— Bombay  Island— China— Chinese  Turkes- 
tan—Japan— -Akita  Prefecture— Prefectures  of  Yamagata,  Aomori  and  Dis- 
trict of  Hokkaido— Australia— New  South  Wales— Western  Australia— North- 


TABLE  OF  CONTENTS  XV 

PAGE 

ern  Territory — Tasmania — New  Zealand — Dutch  East  Indies — Buton  (Boe- 
ten)  Island—Africa— Algeria— Province  of  Oran— Nigeria— Rhodesia— -Mad- 
agascar. 

CHAPTER  X 

ASPHALTITES    2Z7 

GILSONITE  or  UINTAITE— North  America— United  States— Utah— Oregon- 
Asia — Russia — Archangel  Province — GLANCE  PITCH — North  America — West 
Indies — Barbados — Santo  Domingo  (Haiti) — Cuba — Province  of  Pinar  del 
Rio— Province  of  Santa  Clara — Province  of  Camaguey — Mexico — State  of 
Vera  Cruz — United  States — Utah — Central  America — Nicaragua — District 
of  Chontales — Salvador — Department  of  San  Miguel — South  America — 
Colombia — Province  of  Tolima — Province  of  Bolivar — Europe — Germany — 
Bentheim — Syria  (Levant  States) — Vilayet  of  Sham — Palestine — Mesopotamia 
(Iraq) — GRAHAMITE — North  America — United  States — West  Virginia — 
Texas — Oklahoma — Colorado — Mexico — State  of  Vera  Cruz — State  of  San 
Luis  Potosi — State  of  Tamaulipas — Cuba — Province  of  Pinar  del  Rio — Prov- 
ince of  Havana — Province  of  Santa  Clara — South  America — Trinidad — 
Argentina — Province  of  Mendoza — Province  of  Neuquen — Peru — Province  of 
Tarma. 

CHAPTER  XI 
ASPHALTIC  PYROBITUMENS    202 

ELATERITE — England — Derbyshire  County — Australia — State  of  South  Australia 
— Asiatic  Russia — State  of  Turkestan — WURTZILITE — United  States — Utah — 
Albertite — Canada — Province  of  New  Brunswick — Province  of  Nova  Scotia 
— United  States — Utah — South  America — Falkland  Islands — Germany — Prov- 
ince of  Hanover — Australia — Tasmania — Portuguese  West  Africa — Province 
of  Angola— IMPSONITE— North  America—  United  States— Oklahoma— Ar- 
kansas— Nevada — Michigan — South  America — Peru — Provinces  of  Canta 
and  Yauli — Province  of  Huarochiri — Brazil — State  of  Sao  Paulo — Australia 
— West  Australia. 

CHAPTER  XII 
PYROBITUMINOUS  SHALES   275 


PART  1 1  I—TARS  AND  PITCHES 

CHAPTER  XIII 
GENERAL  METHODS  OF  PRODUCING  TARS 278 

Destructive  Distillation — Composition  of  the  Substance — The  Temperature 
— The  Time  of  Heating — The  Pressure — The  Efficiency  of  the  Condensing 
System — Partial  Combustion  with  Air  and  Steam — Partial  Combustion 
with  a  Limited  Access  of  Air— Cracking  of  Oil  Vapors. 


xvi  TABLE  OF  CONTENTS 

CHAPTER  XIV 

PAGE 

WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH  ...................     288 

Wood  Tar  and  Wood-tar  Pitch—  Varieties  of  Wood  Used—  Yields  of 
Distillation  —  Hardwood  Distillation  —  Method  of  Distilling  —  Refining  Proc- 
esses —  Soft  (Resinous)  Wood  Distillation  —  Method  of  Distilling  —  Refining 
Processes  —  Hardwood  Tar  and  Pine  Tar  —  Hardwood-tar  Pitch  and  Pine-tar 
Pitch—Rosin  Pitchr-Raw  Materials  Used—  Methods  of  Distilling—  Products 
Obtained  —  Properties  of  Rosin  Pitch  —  "Burgundy  Pitch." 

CHAPTER  XV 

PEAT  AND  LIGNITE  TARS  AND  PITCHES  ..............................     305 

Peat  Tar  and  Peat-tar  Pitch  —  Formation  of  Peat  —  Varieties  of  Peat  — 
Methods  of  Collecting  —  Dehydrating  Processes  —  Methods  of  Distilling  —  Refin- 
ing Processes  —  Properties  of  Peat  Tar  —  Properties  of  Peat-tar  Pitch  —  Lignite 
Tar  and  Lignite-tar  Pitch  —  Varieties  of  Lignite  —  Mining  Methods  — 
Methods  of  Distilling  —  Products  Obtained  —  Treating  Impure  Lignite  —  Proper- 
ties of  Lignite  Tar  —  Refining  Processes  —  Products  Obtained  —  Properties  of 
Lignite-tar  Pitch. 

CHAPTER  XVI 
SHALE  TAR  AND  SHALE-TAR  PITCH  ....................................       2 


Shale  Mining  —  Retorts  Used  for  Distillation  —  Pumpherston  Retort  —  Hender- 
son or  Broxburn  Retort  —  Methods  of  Recovering  Shale  Tar  —  Products  Ob- 
tained —  Properties  of  Shale  Tar  —  Refining  of  Shale  Tar  —  Properties  of  Shale- 
tar  Pitch. 

CHAPTER  XVII 

COAL  TAR  AND  COAL-TAR  PITCH  ......................................     336 

Bituminous  Coals  Used  —  Temperature  of  Treatment  —  Production  of  Gas- 
Works  Coal  Tar  —  Retorts  Used  —  Methods  of  Recovery  —  Products  Obtained  _ 
Production  of  Coke-oven  Coal  Tar  —  Retorts  Used  —  Methods  of  Recovery  _ 
Products  Obtained  —  Production  of  Blast-furnace  Coal  Tar  —  Methods  of  Re- 
covery —  Production  of  Producer-gas  Coal  Tar  —  Products  Obtained  —  Produc- 
tion of  Low-temperature  Tars—  Products  Obtained—  Properties  of  Coal 
Tars  —  Methods  of  Dehydrating  Coal  Tar  —  Settling  —  Use  of  Cen- 
trifuges—Horizontal Stills—  Tube  Heaters—  Cascade  System—  Methods  of 
Distilling  Coal  Tar  —  Simple  Batch  Stills  —  Vacuum  Distillation  —  Steam  Dis- 
tillation —  Gas  Recirculation  —  Continuous  Stills  —  Tube  Stills  —  Collector- 
Main  Condensers—  Recovery  and  Treatment  of  Coal-tar  Distillates—  Recovery 
and  Treatment  of  Coal-tar  Residuals—  Commercial  Varieties  of  Coal-tar  Pitch 
—Pitch  Coke—  Properties  of  Coal-tar  Pitches—  Gas-works  Coal-tar  Pitches- 
Coke-oven  Coal-tar  Pitch—  Blast-furnace  Coal-tar  Pitch—  Gas-producer  Coal- 
tar  Pitch—  Low-temperature  Coal-tar  Bitch—  Anthracene  Pitch—  Naphthol 
Pitch—  Cresol  Pitch. 


TABLE  OF  CONTENTS  XVii 

CHAPTER  XVIII 

PAGE 

WATER-GAS  AND  OIL-GAS  TARS  AND  PITCHES 378 

Carburetted  Water-gas  Tar — Method  of  Production — Properties  of  Water- 
gas  Tar — Oil-gas  Tars — Methods  of  Production — Pintsch  Gas — Oil-water 
Gas — Blau  Gas — Properties  of  Oil-gas  Tars — Refining  of  Water-gas  and  Oil- 
gas  Tars — Properties  of  Water-gas-tar  Pitch  and  Oil-gas-tar  Pitch. 

CHAPTER  XIX 

FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH 386 

Fatty-acid  Pitch — Sources  from  which  Obtained — Production  of  Candle  and 
Soap  Stocks — Hydrolysis  by  Means  of  Water — Hydrolysis  by  Means  of  Con- 
centrated Sulfuric  Acid — Hydrolysis  by  the  "Mixed  Process" — Hydrolysis  by 
Means  of  the  Sulfo-compounds — Hydrolysis  by  Means  of  Ferments — Refining 
Vegetable  Oils  by  Means  of  Alkali — Refining  of  Cotton-seed  Oil — Refining 
of  Corn-Oil — Refining  Refuse  Greases — Refining  Packing-house  and  Carcass- 
rendering  Greases — Refining  Bone  Grease — Refining  Garbage  and  Sewage 
Greases — Refining  Woolen-mill  Waste — Treatment  of  Wool  Grease — Physical 
and  Chemical  Properties  of  Fatty-acid  Pitches—Bone  Tar  and  Bone-tar 
Pitch — Methods  of  Production — Physical  and  Chemical  Characteristics — 
Glycerine  Pitch. 

PART  IF—PYROGENOUS  ASPHALTS  AND  WAXES 

CHAPTER  XX 

PETROLEUM  ASPHALTS    409 

Varieties  of  Petroleum — Asphaltic  Petroleums — Semi-asphaltic  Petroleums 
— Non-asphaltic  Petroleums — Dehydration  of  Petroleum — Settling — Cen- 
trifuging — Tube-stills — Distillation  of  Petroleum — Batch  Stills — Steam 
Distillation — Dry  Distillation — Continuous  Stills — Tube  or  Pipe  Stills — 
Cracking  Processes — Liquid  Phase  Cracking — Tube-and-tank  Process — 
Cross  Process — Holmes-Manly  Process — Mixed  Phase  Cracking — Burton 
Process — Dubb's  Process — Liquid  Products — Semi-solid  to  Solid  Distillates — 
Semi-solid  to  Solid  Residues — Residual  Oils — Varieties  Obtained — Physical 
and  Chemical  Characteristics — Blown  Petroleum  Asphalts — Processes  Used 
— Advantages  of  "Blowing"  Over  the  Steam-distillation  Process — Physical  and 
Chemical  Characteristics — Sulfurized  Asphalts — Residual  Asphalts — Proc- 
esses Used — Physical  and  Chemical  Characteristics — Methods  of  Distinguish- 
ing  between  Petroleum  Asphalts  and  Native  Asphalts — Sludge  Asphalts — 
Methods  of  Production — Physical  and  Chemical  Characteristics. 

CHAPTER  XXI 

PARAFFIN  WAX,  WAX  TAILINGS  AND  RESINS 466 

Paraffin  Wax — Sources  from  which  Obtained — Physical  and  Chemical  Char- 
acteristics— Wax  Tailings — Methods  of  Production — Physical  and  Chemical 
Characteristics— Petroleum  Resinsr— Asphaltic  Resins. 


XViii  TABLE  OF  CONTENTS 

CHAPTER  XXII 

PAGE 

WURTZILITE   ASPHALT    472 

Method    of    Production — Still    Used — Depolymerization    Process — Grades    of 
Wurtzilite  Asphalt  Produced — Chemical  and  Physical  Characteristics. 


PART  V— MANUFACTURED  PRODUCTS  AND 

THEIR  USES 

CHAPTER  XXIII 

COMPOUNDING  OF  BITUMINOUS  SUBSTANCES 476 

General  Considerations — Hardness,  Fusibility,  Penetration,  Approximate 
Comparative  Volatility,  Weatherproof  Properties  and  Efficiency  of  Fluxing 
of  Various  Bituminous  Substances — Principles  Involved  in  Preparing  Mixtures 
— Binary  Mixtures — Softening  of  the  Substance  and  Lowering  its  Fusing- 
point — Augmenting  the  Adhesive  Properties  of  the  Substance — Increasing  the 
Fluidity  of  the  Substance  when  Melted — Effecting  a  More  Perfect  Union  or 
Blending  of  the  Constituents — Hardening  the  Substance,  Raising  its  Fusing- 
point  and  Increasing  its  Stability — Rendering  the  Mixture  Less  Susceptible  to 
Temperature  Changes — Increasing  the  Tensile  Strength  of  the  Mixture — 
Making  the  Mixture  More  Weatherproof — Rendering  Wax-like,  Unctuous 
to  the  Feel,  or  Lessening  the  Tendency  Towards  Stickiness — Tertiary  and 
Complex  Mixtures — Classes  of  Bituminous  Mixtures — Soft  (Liquid)  Bitumi- 
nous Products — Medium  (Semi-liquid  to  Semi-solid)  Bituminous  Products — 
Hard  (Solid)  Bituminous  Products — Processes  of  Compounding  Bituminous 
Substances. 

CHAPTER  XXIV 

BITUMINOUS    SUBSTANCES    ADMIXED     WITH    DISCRETE    AGGRE- 
GATES        494 

Methods  of  Incorporating  Discrete  Aggregates — Colloidal  Particles — Ad- 
mixed Mechanically — Inorganic — Organic — Liberated  "In  Situ" — Inorganic 
— Organic — Fillers  (Powders)  Including  Pigments — Inorganic — Oxides — 
Silicates — Carbonates — Sulfates — Phosphates — Miscellaneous  Rock  Products 
— Pyrogenous  Products — Black  Pigments — Colored  Pigments — Organic — Vege- 
table Products — Black  Pigments — Fibers — Inorganic — Organic — Granular 
Matter — Inorganic — Organic — Coarse  Mineral  Aggregates — Crushed 
Rock,  Stone,  Gravel  or  Slag — Graded  Aggregates — Combinations  of  the 
Foregoing. 

CHAPTER  XXV 

BITUMINOUS  SUBSTANCES  DISPERSED  IN  WATER 503 

Types  of  Bituminous  Dispersions — Forms  of  Apparatus  Used — Charac- 
ter of  the  Bituminous  Substance — Character  of  the  Dispersing  Agent — 
Inorganic  Substances — Hydroxides — Oxides — Silicates — Sulfates — Phosphates — 
Sulfides  or  Polysulfides — Alkalies — Miscellaneous — Organic  Substances — Fats 


TABLE  OF  CONTENTS  xix 

PAGE 

and  Oils — Resins — Soaps — Sulfonated  Vegetable  Oils — Sulfite  Liquor — Min- 
eral-Oil Derivatives — Carbonaceous  Matter — Alkaline  Bases — Proteins  or  Pro- 
teids — Albumenoids — Pectins — Gums  and  Algae — Polysaccharides  and  Herai- 
celluloses — Tannins — Miscellaneous — Parlous  Combinations — Clay  in  Com- 
bination— Sodium  Silicate  in  Combination — Soaps  in  Combination — Sulfonated 
Vegetable  Oils  in  Combination — Alkaline  Caseinates  in  Combination — Glue  or 
Gelatine  in  Combination — Tannic  Acid  in  Combination — Uses  of  Bitumin- 
ous Dispersions. 

CHAPTER  XXVI 
BITUMINOUS  SUBSTANCES  DISSOLVED  IN  SOLVENTS 514 

Classes  of  Solvents — Function  of  Solvents — Behavior  of  Solvents — Solubility 
of  Bituminous  Substances — Adsorption  of  Bituminous  Substances. 


CHAPTER  XXVII 

SOLID,  SEMI-SOLID  AND  SEMI-LIQUID  BITUMINOUS  COMPOSITIONS.     526 

Adhesive  Compounds  for  Built-up  Roofing  and  Waterproofing  Work — Ad- 
hesive Compounds  for  Waterproofing — Below  Ground — Above  Ground — Ad- 
hesive Compounds  for  Built-up  Roofing  Work — Plastic-slate  Cement — 
Calking  Compounds — Bituminous  Grout — Bituminous  Enamel  for  the  Inside 
of  Steel  Ships — Bituminous  Enamel — Bituminous  Primer — Bituminous  Enamel 
for  Acid-proofing  Concrete  Surfaces — Pipe  Dips  and  Pipe-sealing  Compounds 
— Pipe  Dips — Pipe  Wrappings — Pipe-sealing  Compounds — Electrical  Insulat- 
ing Compounds — Vacuum  Impregnating  Compounds — Cable-splicing  and  Pot- 
head  Compounds — Battery-box  Compounds — "Carbons"  for  Batteries,  Electric 
Lights  and  Armature  Brushes — Bituminous  Rubber  Substitutes — Molded  Com- 
positions— Mixtures  for  Small  Molded  Articles — Preformed  Joints  and  Wash- 
ers— Molded  Brake-linings,  Clutch-facings  and  Friction  Elements — Bitumin- 
ated  Cork  Mixtures — Battery  Boxes — Fibrated  Bituminous  Compositions — 
Roof  Tiles — Floor  Tiles — Floor  and  Step  Treads — Artificial  Lumber  and  Rail- 
road Ties — Pipes  and  Conduits — Burial  Vaults — Phonograph  Records — Bi- 
tuminated  Leather  Mixtures — Briquette  Binders — Core  Compounds — Miscel- 
laneous Bituminous  Products — Bituminous  Fuels — Tars  and  Oils  for  the 
Flotation  of  Ores — Waterproofing  Compounds  for  Portland-cement  Mortar 
and  Concrete — Pure  Bituminous  Substances — Bituminous  Substances  in  Emul- 
sified Form— Methods  of  Use— Sponge  Asphalt— Asphalt  Dust  and  Filaments 
—Asphalt  Jelly. 

CHAPTER  XXVIII 

BITUMINOUS  PAVING  MATERIALS 567 

Bituminous  Binders — Liquid  Asphaltic  Binders— Semi-solid  to  Solid  As- 
phaltic  Binders — Coal-tar  Binders — Cut-back  Products — Bituminous  Emulsions 
—Mineral  Aggregates — Bituminous  Compositions  for  Dust-laying 
(Cold  Application) — Bituminous  Emulsions — Non-emulsified  Products — 
General  Considerations — Bituminous  Surfacings — Surface  Treatment— Silt 
Roads  —  Clay  Roads  —  Sandy  Roads  —  Seal-Coats  —  To  Loose  Surfaces  —  To 
Bonded  Surfaces — To  Old  Bituminous  Surfaces — To  Non-bituminous  Sur- 
faces— Road-Mix  Wearing  Course — Open  Aggregate  ("Macadam  Type") — 


XX  TABLE  OF  CONTENTS 

PAGE 

Dense  Aggregate  ("Graded  Type") — Plant-Mix  Wearing  Course — Open  Ag- 
gregate ("Macadam  Type")-— Dense  Aggregate  ("Graded  Type")— Bitumi- 
nous Macadam  Pavements — Foundation — Base  Course — Surface  Course — 
Bituminous  Emulsions — Penetration  Method — Road-Mix  Method — Bitumi- 
nous Concrete  Pavements — Foundation — Base  Course  ("Black-base")  — 
Surface  Course,  Coarsely-graded  Type — Surface  Course,  Finely-graded  Type 
— Asphalt  Emulsions — Sheet-asphalt  Pavements — Foundation — Binder  and 
Surface  Courses — General  Considerations — Bituminous  Joint-Fillers — Fill- 
ing the  Joints — Asphalt-block  Pavements — Foundation — Laying  the  Blocks 
— Bituminized  Wood-block  Pavements — Methods  of  Impregnation — Creo- 
sote Preservatives — Foundation — Cushion  Layer — Filling  the  Joints — General 
Considerations — Asphalt  Mastic  Foot-Pavements  and  Floors — Asphalts 
Used — Methods  of  Preparation — Methods  of  Application — Asphalt  Mastic 
Roofs — Bituminous  Expansion  Joints — Promolded  Strips — Bituminized 
Fabric  Strips — Laminated  Strips — Armored  Strips — Bituminous  Rail-fillers 
— Asphalt  Bridge-planking— Bituminous  Revetment. 

CHAPTER  XXIX 

BITUMINIZED  FABRICS,  FELTS  AND  PAPERS  FOR  ROOFING,  FLOOR- 
ING, WATERPROOFING,  BUILDING  AND  INSULATING  PURPOSES     617 

Prepared  Sheet  Roofings — Felted  Fabrics — Rag-felt — Methods  of  Fire- 
proofing  Rag-felt — String-felt  or  Threaded-felt — Asbestos  Felt — Woven  Fa- 
brics— Bituminous  Saturating  Compositions — Asphaltic  Products — Tar  Prod- 
ucts— Bituminous  Coating  and  Adhesive  Compositions — Fillers — Black  Pig- 
ments— Colored  Pigments — Inorganic  Surfacings — Fine  Mineral  Particles — 
Moderately  Coarse  Mineral  Granules — Coarse  Mineral  Granules — Organic 
Surfacings — Saturated  Felt — Saturating  the  Fabric — Tarpaulins — Brattice 
Cloth — Tents  and  Awnings — Waterproof  Membranes — Wrapping  Cloth — 
Teredo-proof  Coverings — Roof  Coverings  for  Railway  Cars — Prepared  Roll- 
roofings — Single-layered  Prepared  Roofings — Laminated  Roofings — Decora- 
tive Roll-roofings — Scalloped  and  Serrated  Roll-roofings — Asphalt  Shingles 
— General  Features — Features  Pertaining  to  Thickness — Shingles  Surfaced 
with  Mineral  Granules — Rear  Surface  Coating — Shingles  Surfaced  with  Min- 
eral Granules  and  Coated  with  Hydraulic  Cement — Shingles  Surfaced  with 
Slate-veneer  or  Tile  or  Asbestos-cement — Shingles  Surfaced  with  Metals — 
Shingles  Reinforced  with  a  Core  of  Sheet-metal  or  Wire — Laminated  Shingles 
— Combinations  with  Asbestos  Felt — Combinations  Involving  the  Use  of 
Wooden  Shingles — Miscellaneous  Forms — Individual  Shingles — Forming 
Rectangular  Patterns  when  Laid — Forming  Diamond-shaped  Patterns  when 
Laid — Forming  Hexagonal  Patterns  when  Laid — Forming  Octagonal  Patterns 
when  Laid — Forming  Circular  Patterns  when  Laid — Forming  Thatched  Ef- 
fects when  Laid — Reversible  Forms — Strip  Shingles — Forming  Rectangular 
Patterns  when  Laid — Forming  Diamond-shaped  Patterns  when  Laid — Form- 
ing Hexagonal  Patterns  when  Laid — Forming  Octagonal  Patterns  when  Laid 
— Forming  Circular  or  Curved  Effects  when  Laid — Forming  Thatched  Effects 
when  Laid — Forming  Miscellaneous  Patterns  when  Laid — Reversible  Forms — 
Asphalt  Sidings — Fastening  Devices — Lap-cement — Nails — Metal  Cleats  for 
Roll-roofings — Concealed  Nailing  for  Roll-roofings — Forming  Standing  Seams 
— Methods  of  Packaging — Methods  of  Laying  Roofings  and  Shingles — Laying 
the  Fabric  in  a  Single  Course — Built-up  Roofs — Laying  Asphalt-shingle 
Roof  a — Fire-resisting  Properties  of  Prepared  Roofings  and  Shingles — Bi-, 


TABLE  OF  CONTENTS  xxi 

PAGE 

tuminized  Floor  Coverings — Saturated  Felt  Base — Method  of  Printing — 
Waterproofing  Membranes — Materials  Used — Preparing  the  Underly- 
ing Surface — Selecting  and  Installing  the  Waterproofing  Membrane — Pro- 
tecting the  Waterproofing  Membrane — Insulating  and  Building  Papers — 
Raw  Paper  Stock — Bituminous  Saturation — Bituminous  Coating  Compositions 
— Method  of  Manufacture — Bituminized  Papers  for  Electrical  Insulation 
— Bituminized  Papers  for  Wrapping  and  Packing  Purposes — Bitumin- 
ized Papers  for  Mulching  Plants  and  Crops— Blasting  Fuses — Bi- 
tuminized Cords  and  Ropes — Insulation  for  Electrical  Transmission 
Wires — Bituminized  Fiber  Conduits — Asphalt  Pipes — Brake  Linings 
and  Clutch-facings  for  Automobiles — Insulating  and  Acoustical  Felts 
for  Automobiles — Electrical  Insulating  Tape — Bituminized  Wall- 
Board — Bituminous  Insulating  Board — Acoustical  Blocks — Bitum- 
inous Stucco-base  and  Plaster-board* 

CHAPTER  XXX 

BITUMINOUS    LACQUERS,     CEMENTS,     VARNISHES,     ENAMELS    AND 

JAPANS    720 

Bituminous  Lacquers  and  Paints — Nature  of  the  Base — Nature  of  the  Fill- 
ers and  Pigments — Nature  of  the  Solvents — Methods  of  Manufacture — Types  , 
of  Bituminous  Paints — Masonry  Coatings — Clear  Damp-proofing  Paints — 
Black  Damp-proofing  Paints — Stone  Backing — Paints  for  Resurfacing  Prepared 
Roofings  —  Asphalt  Fibrous-Roof-Coating  —  Acid-resisting  Coatings — Bitumi- 
nous Coatings  for  Metal  or  Wood — Anti-fouling  Paints — Bituminous  Emulsion 
Paints — Flooring  Compositions  for  Cold  Application — Bituminous  Cements 
— Method  of  Manufacture — Method  of  Use — Bituminous  Varnishes — 
Method  of  Manufacture — Bituminous  Enamels — Method  of  Manufacture — 
Cellulose-Ester  Lacquers — Bituminous  Japans — Method  of  Manufacture 
—Uses. 

PART  VI— METHODS  OF  TESTING 
CHAPTER  XXXI   * 

SAMPLING   757 

General  Methods — Definitions — Sampling  Crude,  Refined  and  Blended  Bi- 
tuminous Substances — Sampling  at  Place  of  Manufacture — When  Material 
is  Pumped  under  Pressure — When  Materials  Flow  by  Gravity — Sampling  at 
Point  of  Delivery — Semi-solid  or  Solid  Materials — Liquid  Materials — Solid 
Bituminous  Materials  in  Crushed  Fragments  or  Powder — Sampling  Bitumi- 
nous Paving  Materials — Sampling  Bituminized  Fabrics— Sampling 
Bituminous  Lacquers,  Cements,  Varnishes  and  Japans,  also  Bitumi- 
nous Emulsions. 

CHAPTER  XXXII 

EXAMINATION  OF   CRUDE,   REFINED   AND   BLENDED  BITUMINOUS 

SUBSTANCES     776 

Synoptical  Table  of  Bituminous  Substances— Physical  Characteristics — 
Color — Color  in  Mass — Color  in  Solution — Homogeneity — To  the  Eye — Under 
Microscope — When  Melted — In  Solution — Appearance  Surface  when  Aged — 


xxii  TABLE  OF  CONTENTS 

PAGE 

Fracture — Lustre — Streak — Water  Absorption — Diffusibility — Specific  Gravity 
—Hydrometer  Method— Westphal  Balance  Method— Bottle  Method— Pyk- 
nometer  Method— Analytical  Balance  Method— Voids  (Entrapped  Air)— Col- 
loidal Capacity-^Clzy  Dispersions — Ultramicroscopic  Count  of  Colloidal  Par- 
ticles—Mechanical Tests— Viscosity— Engler  Method— Saybolt  ( Furol) 
Method  —  Absolute  Viscosity  —  Hutchinson's  Method  —  Float  Test  —  Schutte 
Method— Falling  Ball  Method— Alternating  Stress  Method— Falling  Coaxial 
Cylinder  Method — Hardness  or  Plasticity — Moh's  Scale — Penetrometer — Con- 
sistometer— Susceptibility  Index— Ductility— Dow' s  Method— Author's  Method 
— Tensile  Strength  ( Cohesiveness) — Author's  Method — Adhesiveness — 
Riehm's  Method — Wedmore's  Method — Brown's  Method — Surface  Tension — 
Nellensteyn's  Method— Interfacial  Tension— Thermal  Tests—  Thermal  Con- 
ductivity— A.S.T.M.  Method — Specific  Heat — Heat  Content — Thermal  Ex- 
pansion— A.S.T.M.  Method — Breaking  Point — Knife  Test — Reeve  and  Yea- 
ger's  Method— Fraas  Method— Solidifying-Point—MetzgeT's  Method— Soften- 
ing-Point or  Fusing-Point — Kramer-Sarnow  Method — Ring-and-Ball  Method 
—Cube  Method— Compression  Method— A.S.T.M.  Method  for  Petrolatum— 
A.S.T.M.  Method  for  Paraffin  Wax— Flow-Point— Richardson's  Method— 
Liquefying-Point—  Ubbelohde's  Method—  Twisting-Point— Taylor's  Method— 
Volatile  Matter— A.S.T.M.  Method— Evaporation  Test— A.S.T.M.  Method— 
Distillation  Test— A.S.T.M.  Method— FW/-/>o*w/— Pensky-Martens  Tester- 
Cleveland  Tester— Tag  Closed  Tester— Tag  Open  Tester— Burning-Point- 
Fixed  Carbon— Solubility  Tests— Solubility  in  Carbon  Bisulfide— Where 
the  Constituents  are  Not  to  be  Examined  Further— Where  the  Constituents  are 
to  be  Examined  Further — Carbenes — Richardson's  Method — Solubility  in 
Petroleum  Naphtha— Insoluble  in  Benzol  ("Free  Carbon")— Solubility  in 
Other  Solvents— Chemical  Tests—  Water— Substances  Distilling  at  Low  Tem- 
peratures—Substances Distilling  at  High  Temperatures— Elemental  Composi- 
tion— Carbon— Hydrogen— Sulfur— Nitrogen— Oxygen  (in  Non-mineral  Mat- 
ter)—Molecular  Weight— Freezing-point  Method—  Tar  Adds— Contraction 
Method— Liberation  Method— Naphthalene— Solid  Paraffins— Holders  Method 
—Sulfonation  Residue— Residue  Insoluble  in  Concentrated  Sulfuric  Acid- 
Residue  Insoluble  in  Water— Dimethyl  Sulfate  Method— Formolite  Reaction— 
Nastjukoff  Method— Degree  of  Mercuration—Saponifiable  Constituents— Free 
Acids  (Acid  Value)— Lactones  and  Anhydrides  (Lactone  Value)— Neutral 
Fats  (Ester  Value)— Saponification  Value— Separation  of  Saponifiable  Con- 
stituents—Examination of  Unsaponifiable  Constituents— Examination  of  Sa- 
ponifiable Constituents— Glycerol— ^/>^//*V  Constituents— Free  Asphaltous 
Acids— Asphaltous  Acid  Anhydrides— Asphaltenes— Asphaltic  Resins— Oily 
Constituents— Diazo  Reaction— Graefe's  Method— Anthraquinone  Reaction— 
Liebermann-Storch  Reaction— Colorimetric  Method. 

CHAPTER  XXXIII 

EXAMINATION    OF    BITUMINOUS    SUBSTANCES    COMBINED    WITH 

DISCRETE  AGGREGATES    IOI7 

Physical  Tests  of  Finished  Product— Pawing  Compositions,  Asphalt  Mas- 
tic Bituminous  Grouts,  Pipe-sealing  Compounds,  etc.— Specific  Gravity- 
Voids— Resistance  to  Moisture— Effect  of  Water  on  Adhesion— Hardness— Re- 
sistance to  Displacement— Extrusion  of  Binder  Under  Pressure— Resistance  to 
Impact— Brittleness  or  Shatter  Test— Coefficient  of  Wear— Molded  Materials— 
Thickness— Resistance  to  Moisture— Tensile  Strength— Compressive  Strength— 


TABLE  OF  CONTENTS  xxiii 

PAGE 

Flexural  Strength — Distortion  Under  Heat — Softening-Point — Resistance  to  Im- 
pact— Electrical  Tests — Separation  of  Finished  Product  into  Its  Compo- 
nent Parts — Separation  of  the  Bituminous  Matter  and  Discrete  Aggre- 
gate— Methods  Suitable  for  Aggregates  Associated  with  an  Asphaltic  Binder 
— Hot  Extraction  Method — Cold  Extraction  Method — Centrifugal  Extraction 
Method — Method  Suitable  for  Aggregates  Associated  with  Coal-tar  Pitch 
Binder — Recovery  and  Examination  of  Extracted  Bituminous  Matter — 
Separation  of  Bituminous  Constituents — Examination  of  the  Separated 
Aggregate — Inorganic  Aggregates — Granularmetric  Analysis — Elutriation 
Test — Air-separation  Test — Adsorptive  Capacity  of  Fine  Fillers — Specific 
Gravity — Organic  Particles^  Fiberst  Fillerst  etc. 


CHAPTER  XXXIV 

EXAMINATION  OF  BITUMINIZED   FABRICS 1072 

Physical  Tests  of  the  Finished  Product— Weight  per  Unit  Area— For 
Saturated  Felted  and  Woven  Fabrics — For  Smooth-roll  and  Mineral-surfaced 
Roll-roofing — For  Mineral-surfaced  Shingles — Thickness — Strength — Tensile 
Strength — Bursting  Strength — Tearing  Strength — Pliability — Mandrel  Test — 
Reeve  and  Y eager  Test — Resistance  to  Dampness — Water  Absorption — Resis- 
tance to  Heat — For  Asphalt-saturated  Fabrics — For  Coal-tar  Saturated  Fabrics 
Only — For  Asphalt  Roll-roofings  and  Shingles — Electrical  Tests — Special 
Tests  Applicable  to  Insulating  Tape — Tensile  Strength — Adhesion — Oven 
Test — Tackiness — Separation  of  Finished  Product  into  Its  Component 
Parts — Separation  of  Bituminous  Matter,  Mineral  Matter  and  Fibrous 
Constituents — Moisture — Analysis  of  Saturated  Fabrics  (Single-layered)  — 
Analysis  of  Saturated  and  Coated  Fabrics  (Single-layered) — Recovery 
and  Examination  of  Extracted  Coatings  and  Saturation — Ex- 
amination of  the  Separated  Mineral  Surfacing  and  Admixed  Min- 
eral Constituents — Examination  of  the  Separated  Fabric — Weight  per 
Unit  Area  ("Number") — Uncorrected  Number — Moisture — Corrected  Number 
— Thickness — Tensile  Strength — Porosity — Speed  with  which  the  Felt  Will 
Saturate — Vertical  Method — Horizontal  Method — Saturating  Capacity — Fiber 
Composition. 

CHAPTER  XXXV 

EXAMINATION  OF  BITUMINOUS  SOLVENT  COMPOSITIONS 1117 

Physical  Tests  of  the  Finished  Product— RSsumt  of  Physical  Tests— Spe- 
cific Gravity — Viscosity — Plasticity  and  Mobility — Flash-point — Spreading 
Capacity  and  Workability — Draining  Test — Time  of  Drying — Hiding  Power 
— Color — Gloss — Hardness,  Abrasion  and  Adhesion — Water  Absorption — Re- 
sistance to  Heat — Resistance  to 'Oil — Resistance  to  Acids  and  Alkalies — Dielec- 
tric Strength — Estimation,  Recovery  and  Examination  of  the  Solvent — 
Estimation  and  Recovery  of  Solvent — Evaporation  Method — Steam  Distillation 
Method — Examination  of  the  Solvent — Estimation,  Recovery  and  Exam- 
ination of  Pigment  and  Filler — Estimation  and  Recovery  of  Pigment  and 
Filler— Examination  of  the  Pigment  or  Filler— Estimation,  Recovery  and 
Examination  of  the  Base — Estimation  and  Recovery  of  the  Base — Examina- 
tion of  the  Base. 


xxiv  TABLE  OF  CONTENTS 

CHAPTER  XXXVI 

PAGE 

EXAMINATION  OF  BITUMINOUS  DISPERSIONS 1 132 

Physical  Tests  of  the  Finished  Product— Method  of  Identification— 
Homogeneity — Appearance  Under  Microscope — Sieve  Test — Settlement  Test — 
Stability  on  Aging — Viscosity — Demulsibility — Calcium-chloride  Test — Fer- 
rous-sulfate  Test— Behavior  with  Aggregate  ("Coating  Test")—Miscibility 
with  Water— Effects  on  Freezing— Resistance  to  Water  After  Setting— With- 
out Aggregate— When  Mixed  with  Aggregate— Separation  of  the  Disper- 
sion into  its  Component  Parts— Distillation  Residue—Water  and  Volatile 
Oils— Dispersing  Agents. 

CHAPTER  XXXVII 

WEATHERING  TESTS   "47 

Effects  of  Weathering—Evaporation—Oxidation—Carbonization—Poly- 
merization—Effects of  Moisture— Actual  Weathering  Test— Testing  Bitu- 
minized  Fabrics — Testing  Bituminous-solvent  Compositions — Testing  Crude, 
Refined  or  Blended  Bituminous  Substances— Accelerated  Weathering  Test 

Testing  Bituminized   Fabrics — Testing   Bituminous-solvent   Compositions — 

Testing  Bituminous  Compositions — Modified  Accelerated  Weathering 
Test. 

TEMPERATURE  CONVERSION  TABLE 1182 

BIBLIOGRAPHY    "*3 

REFERENCES    I23 1 

INDEX    '435 


ASPHALTS  AND  ALLIED  SUBSTANCES 


PART  I 
GENERAL  CONSIDERATIONS 


CHAPTER  I 
HISTORICAL  REVIEW 

Origin  of  the  Words  "Asphalt,"   "Bitumen"  and   "Pitch." 

The  word  "asphalt"  is  claimed  to  have  been  derived  from  the 
Accadian  term  "asphaltu"  or  "sphallo,"  meaning  "to  split."  It  was 
later  adopted  by  the  Homeric  Greeks  in  the  form  of  the  adjective 
dcr^aX^,  c's,  signifying  "firm,"  "stable,"  "secure,"  and  the  correspond- 
ing verb  dcr<£aAi£a>,  tiro),  meaning  "to  make  firm  or  stable,"  "to  se- 
cure." It  is  a  significant  fact  that  the  first  use  of  asphalt  by  the 
ancients  was  in  the  nature  of  a  cement  for  securing  or  joining 
together  various  objects,  and  it  thus  seems  likely  that  the  name  itself 
was  expressive  of  this  application.  From  the  Greek,  the  word 
passed  into  late  Latin,  and  thence  into  French  ("asphalte")  and 
English  ("asphalt"). 

The  expression  "bitumen"  originated  in  the  Sanskrit,  where  we 
find  the  words  "jatu,"  meaning  "pitch,"  and  "jatu-krit,"  meaning 
"pitch  creating,"  "pitch  producing"  (referring  to  coniferous  or  res- 
inous trees).  The  Latin  equivalent  is  claimed  by  some  to  be  origi- 
nally "gwitu-men"  (pertaining  to  pitch),  and  by  others,  "pixtumens" 
(exuding  or  bubbling  pitch),  which  was  subsequently  shortened  to 
"bitumen,"  thence  passing  via  French  into  English.  From  the  same 
root  is  derived  the  Anglo  Saxon  word  "cwidu"  (Mastix),  the 
German  word  "Kitt"  (cement  or  mastic)  and  the  old  Norse  word 
"kvada." 


2  HISTORICAL  REVIEW  I 

The  following  terms  have  been  traced  throughout  the  various 
ancient  languages: 

Sumerian: 

Esir  (petroleum  and  native  asphalt) ;  esir-lah  (hard,  glossy 
asphalt) i ;  esir-harsag  (rock  asphalt) ;  esir-e-a  (mastic  asphalt) ;  se- 
li-ud  (pine  tar) ;  kunin  or  esir-ud-du-a  (pitch). 

Sanskrit: 

Jatu  (native  asphalt  also  pitch)  ;  sila-jatu  or  asmajatam-jatu 
(rock  asphalt). 

Assyrian  and  Accadian: 

Iddu,  ittu,  it-tu-u,  or  amaru  (native  asphalt) ;  kukru  or  kir-kir- 
anu  (pine  tar) ;  sippatu  or  kupru  or  ku-pur  (pitch).  In  Babylonia, 
pitch  is  still  termed  "kupru." 

Hebrew : 

Zephet  or  hemar  (native  asphalt)  ;  zephet  or  kopher  or  kofer 
(pitch).  In  Exodus  (II,  3)  we  find  the  words  "hemar"  and 
"zephet"  denoting  pitch. 

Arabic  and  Turkish: 

Seyali  or  zift  or  zipht  (native  asphalt)  ;  chemal  or  humar  (hou- 
mar)  or  gasat  (qasat)  (rock  asphalt) ;  ghir  or  gir  or  kir  or  kafr 
(mastic  asphalt) ;  zipht  or  kir  or  kafr  (pitch) ;  neftgil  (mineral 
wax). 

Greek: 

Maltha  (soft  asphalt) ;  asphaltos  (native  asphalt) ;  pissasphal- 
tos  or  pittasphaltos  or  pittolium  (rock  asphalt)  ;  pissa-hygra  or 
pisselaion  (pine  tar)  ;  pissa  or  pitta  (pitch)  ;  ampelitis  (mineral 
wax  and  asphaltites) ;  spinos  (bituminous  coal)  ;  anthrax  (anthra- 
cite coal). 

La  tin : 

Maltha  or  bitumen  liquidum  (soft  asphalt);  bitumen  (native 
asphalt) ;  pixliquida  or  serum  picis  (pine  tar) ;  pix  (pitch) ;  gagates 
(asphaltite  and  jet  and  lignite) ;  lapis  thracius  (bituminous  coal) ; 
carbo  (anthracite  coal). 

Fossils  Preserved  by  Means  of  Asphalt.  One  of  the  most  in- 
teresting cases  on  record  is  in  connection  with  the  fossilized  remains 
of  plants  and  animals  recovered  from  the  Rancho-la-Brea  asphalt 
pits  in  Los  Angeles  County,  California,  about  eight  miles  from  the 
City  of  Los  Angeles.1  These  consist  of  a  series  of  crater-like  pits, 


I  FOSSILS  PRESERVED  BY  MEANS  OF  ASPHALT  3 

generally  disconnected,  now  filled  with  asphalt,  from  which  a  variety 
of  prehistoric  flora  and  fauna  have  been  excavated,  including  the 
trunks  of  trees,  pine  cones,  acorns,  mastodons,  woolly  mammoths, 
elephants,  the  ancient  ox,  giant  sloth,  camel,  saber-toothed  tiger, 
lion,  horse,  wolf,  cave  bear,  and  numerous  species  of  vultures  and 


w .  '.i 


Courtesy    i-/os   /\ngcies  museum. 


FIG.  2. — Cypress  Tree  Preserved  by  Asphalt  for  25,000  Years,  Rancho-Ia-Brea  Asphalt 

Pits,  California. 

carnivorous  birds,  all  now  extinct.  The  theory  has  been  advanced 
that  the  pits  were  originally  formed  by  "blow-outs'*  of  gas  from  an 
underlying  oil  deposit,  forming  surface  craters  of  funnel-like  shape, 
filled  by  an  inflow  of  soft,  sticky  asphalt,  which  in  time  became 
quiescent,  possibly  crusting  over,  but  deadly  to  any  form  of  beast 


HISTORICAL  REVIEW 


that  stepped  into  them.  Once  mired  in  the  asphalt,  the  victim's 
struggles  would  only  sink  it  deeper  and  attract  a  host  of  carnivores 
to  the  feast.  These  in  turn  would  only  contribute  so  many  more 
victims  to  the  insatiable  greed  of  the  trap.  Then  came  carrion 
eaters,  vultures,  eagles  and  many  others,  which  contributed  avian 


Courtesy  Los  Angeles  Museum. 

FIG.  3. — Bones  of  Pre-historic  Animals  Excavated  from  Rancho-la-Brea  Asphalt  Pits. 

remains  to  the  mass.  An  artist's  conception  of  the  "Death  Trap" 
of  Rancho-la-Brea  is  illustrated  in  Fig.  i.  The  skeletons  have  been 
preserved  perfectly  by  the  asphalt.  They  have  been  identified  by 
archeologists  as  belonging  to  the  pleistocene  or  glacial  period,  which 
according  to  authorities  terminated  about  25,000  years  ago,  or 
long  before  the  advent  of  man. 


I  USE  OF  ASPHALT  BY  THE  SUMER1ANS  5 

Figure  2  shows  the  trunk  of  a  pleistocene  cypress  found  in  one 
of  the  pits  in  an  upright  position,  packed  solidly  about  with  bones 
of  the  aforementioned  animals,  and  preserved  in  almost  its  original 
state  by  the  asphalt  which  surrounded  it.  This  represents  one  of 
the  oldest  specimens  of  wood  in  existence  and  bears  mute  evidence 
of  the  remarkable  preservation  properties  of  asphalt. 

Figure  3  shows  a  mass  of  prehistoric  elephant  bones,  as  they  were 
being  excavated  from  the  asphalt  in  an  adjacent  pit.  In  no  other 
known  mineral  deposits  are  the  bones  of  these  huge  beasts  preserved 
as  well  as  in  the  asphalt  beds  of  Rancho-la-Brea.  A  smaller  deposit 
of  a  similar  character  has  been  found  near  McKittrick,  Cal.2 

Use  of  Asphalt  by  the  Sumerians  (about  3800  to  2500  B.C.)-3 
The  earliest  recorded  use  of  asphalt  by  the  human  race  was  by  the 
pre-Babylonian  inhabitants  of  the  Euphrates  Valley  in  southeastern 
Mesopotamia,  the  present  Iraq,  formerly  called  Sumer  and  Accad 
(Akkad),  and  later  Babylonia.  In  this  region,  between  the  river 
Nile  in  Egypt  and  the  Indus  river  in  India,  there  occur  various  de- 
posits of  asphalt  as  illustrated  in  Fig.  4.  The  following  historical 
data  have  been  recorded: 

King  Sargon  of  Accad  (about  3800  B.C.}.  A  legend  has  come 
down  through  the  ages  that  King  Sargon,  while  an  infant,  was 
placed  in  a  reed  basket  coated  with  asphalt,  by  his  mother  Itti-Bel,  a 
Priestess,  and  set  adrift  on  the  waters  of  the  Euphrates  river  during 
one  of  its  frequent  overflows.4  This  corresponds  closely  with  the 
tale  of  Moses,  later  appearing  in  the  Bible. 

Manishtusu,  King  of  Kish  (about  3600  B.C.}.  The  bust  of 
this  early  Sumerian  ruler  was  found  in  the  course  of  excavations 
at  Susa,  in  Persia,  whence  it  is  supposed  to  have  been  carried  by  an 
Elamite  conqueror  in  the  twelfth  century  B.C.5  In  describing  this 
statue,  M.  J.  de  Morgan  states ;  "the  eyes,  composed  of  white  lime- 
stone, once  ornamented  with  black  pupils  now  fallen  off,  are  held  in 
their  orbits  with  the  aid  of  bitumen9,  the  face  appears  rough;  the 
beard  and  hair  are  of  conventional  design;  as  regards  the  inscrip- 
tion, it  is  engraved  in  lineal  cuneiform  characters  of  the  most  ancient 
style."  The  original  is  at  the  Louvre  and  is  illustrated  in  Fig.  5. 

Ornaments  (about  3500  B.C.}.  Fragments  of  a  ring  com- 
posed of  asphalt  have  been  unearthed  above  the  flood  layer  of  the 
Euphrates  at  the  site  of  the  prehistoric  city  of  Ur  in  southern  Baby- 


HISTORICAL  REVIEW 


FIG.  4. — Asphalt  Deposits  between  Nile  and  Indus  Rivers. 


I  USE  OF  ASPHALT  BY  THE  SUM  BRIANS  7 

Ionia,  ascribed  to  the  Sumerians  of  about  3500  B.C.6    Upon  analy- 
sis it  was  found  to  consist  of  the  following: 

Soluble  in  pyridine 63.7  per  cent 

Ash  recovered  from  pyridine  extract   3.8  per  cent 

Ash  not  removed  by  pyridine   27.4  per  cent 

CO2  equivalent  to  CaO  in  ash   1.9  per  cent 

Organic  matter  (by  difference) 3.2  per  cent 

Total    100.0  per  cent 

The  mineral  constituents  were  composed  of  5  i  per  cent  silica  (sand, 
diatoms,  foraminifera  and  cells)  and  34  per  cent  CaSO4. 


From  "The  Civilization  of  Babylonia  and  Assyria,"  J.  B.  Lippincott  Co. 
FIG.  5. — Bust  of  Manishtusu,  King  of  Kish  (3600  B.C.)   with  Eyes  Set  in  Asphalt. 

An  interesting  ornament  has  been  excavated  from  one  of  the 
graves  of  a  Sumerian  King  at  Ur  7  consisting  of  a  statue  of  a  ram 


8 


HISTORICAL  REVIEW 


dating  back  to  3500-3100  B.C.  as  illustrated  in  Fig.  6.  The  head 
and  legs  of  the  ram,  also  the  tree-trunk  are  carved  out  of  wood  over 
which  gold  foil  has  been  cemented  by  means  of  asphalt.  The  back 
$nd  flanks  of  the  ram  are  coated  with  asphalt  in  which  hair  has  been 
embedded. 

At  Tell-Asmar  in  Eshnunna  (3200  to  2900  B.C.).    Excavations 


(From  F.  A.  Brockman,  Leipzig.    Courtesy 
of  New  York  Public  Library) 

FIG.  6.— Sumerian  Statue  of  a  Ram  (3500-3100  B.C.) 

in  1931  at  Tell-Asmar,  50  miles  northeast  of  Baghdad,  on  the 
eastern  bank  of  Diyala  river  (which  joins  the  Tigris  river  directly 
south  of  Baghdad)  have  revealed  the  use  of  asphaltic  mastic  by  the 
Sumerians  for  building  purposes.8  Similarly,  at  Khafaje,  in  the 
same  vicinity,  excavations  have  uncovered  floors  composed  of  a  layer 
of  asphalt  mastic  3  to  6  cms.  thick,  likewise  clay  bricks  bonded 
together  with  asphalt  mastic.  This  mastic  has  been  identified  as 


USE  OF  ASPHALT  BY  THE  SUMERIANS 


9 


asphalt  (probably  originating  in  the  vicinity  of  Hit),  mineral  filler 
(loam,  limestone  and  marl)   and  vegetable  fibers   (straw).     This 


FIG.  7. — Babylonian  Pavements  Excavated  at  Tell-Asmar. 


FIG.  8. — Babylonian  Stair  Treads  at 
Tell-Asmar. 


FIG.  9.— Babylonian  Baths  Waterproofed 
with  Asphalt-Mastic  at  Tell-Asmar. 


composition  was  used  for  bonding  bricks  in  the  construction  of 
buildings  and  pavements  (Fig.  7)  ;  for  protecting  exterior  masonry 
surfaces;  for  troweling  over  the  surface  of  interior  floors  and 


10 


HISTORICAL  REVIEW 


stair   treads    (Fig.    8);   and   for   waterproofing  baths    (Fig.   9), 
drains,  etc.® 

Lugal-daudu,  King  of  Adab  (about  3000  B.C.).  In  1903-4, 
Dr.  E.  J.  Banks,  while  excavating  at  Adab  (known  also  as  Bismaya, 
between  the  EuhctifiOJldJDuH^^  a  marble  statue 


of  and  J*  Co* 

FIG.  10. — Statue  of  Lugal-daudu,  King  of  Adab  (3000  B.C.)   Showing  Eyesockets  Lined 

with  Asphalt. 

of  Lugal-daudu,  King  of  Adab  (Fig.  10),  one  of  the  early  Sumer- 
ian  rulers,  who  lived  about  3000  B.C.10  An  inscription  reveals 
the  name  of  the  city  of  Adab.  The  eyesockets  are  hollow,  and 
still  show  the  presence  of  asphalt,  indicating  that  they  were 
once  inlaid  with  some  substance,  probably  ivory  or  mother-of- 
pearl.  The  statue  is  now  on  exhibition  at  the  Ottoman  Museum 
in  Istanbul.11 


USE  OF  ASPHALT  BY  THE  SUMERIANS 


11 


Another  statue  (Fig.  n)  originating  about  the  same  time  (3000 
B.C.),  known  as  the  "Human-Headed  Bull,"  is  composed  of  black 
steatite,  inlaid  with  small  yellow  shells  imitating  streaks,  and  held  in 
place  with  asphalt.  Many  of  the  shells  are  intact,  gripped  firmly  by 
the  asphalt  throughout  fifty  centuries  of  time  and  exposure,  thus 
furnishing  evidence  of  its  remarkable  adhesiveness  and  durability. 
This  statue  is  now  at  the  Louvre,  Paris.12 


From  "The  Civilization  of  Babylonia  and  Assyria,"  J.  B.   Ltppincott  Co. 
FIG.  ii. — Human-Headed  Bull  (3000  B.C.)  with  Shells  Inlaid  in  Asphalt. 

Entemena  of  Shirpula  (about  2850  B.C.).  An  interesting  spec- 
imen of  Sumerian  art  was  excavated  at  Lagash,  near  the  mouth  of 
the  Euphrates,  consisting  of  a  sculptured  votive  offering  dating  back 
to  Entemena,  ruler  or  so-called  "Patesi"  of  Shirpula  (2850  B.C.), 
This  bears  as  an  inscription,  the  heraldic  device  of  Lagash,  by 
means  of  which  we  are  enabled  to  fix  its  date  and  origin.  The  tablet 


12 


HISTORICAL  REVIEW 


is  an  artificial  composition  of  clay  and  asphalt  (Fig.  12).    It  is  also 
on  exhibition  at  the  Louvre.13 

Ur-Nind,  King  of  Lagash  (about  2800  B.C.).  In  the  city  of 
Kish  (Persia)  there  has  been  excavated  the  palace  of  King  Ur-Nina, 
the  foundations  of  which  consist  of  plano-convex  bricks  cemented 
together  with  asphalt  mortar.  Similarly,  in  the  ancient  city  of  Nip- 
pur (about  60  miles  south  of  Baghdad)  excavations  show  Sumer- 
ian  structures  dating  from  this  same  period,  composed  of  natural 


From  "The  Civilization  of  Babylonia  and  Assyria,"  J.  B.  Lippincott  Co. 
FIG.  12. — Heraldic  Device  of  Lagash  (2850  B.C.)   Cast  in  Asphalt. 

stones  joined  together  with  asphalt  mortar,  including  the  "ziggurat" 
of  Enlil. 

Ornaments  and  Sculptured  Objects  (2800  to  2500  B.C.). 
A  number  of  specimens  of  sculpture  involving  the  use  of  asphalt 
were  excavated  at  Susa  in  the  province  of  Susiana,  by  M.  J.  de 
Morgan's  expedition  of  Paris.14  These  are  in  an  excellent  state 
of  preservation,  and  by  the  inscriptions  and  characteristic  orna- 


USE  OF  ASPHALT  BY  THE  SUMERIANS 


13 


mentation   are  supposed  to   have   originated   between    2800   and 
2500  B.C. 

Figure  13  shows  various  small  animals  carved  of  alabaster 
having  the  eyes  cemented  in  place  with  asphalt;  Fig.  14,  two  decor- 
ated vases  composed  wholly  of  asphalt;  and  Fig.  15,  a  sculpture 


From  "Memoires  de  la  Delegation  en  Perse,"  by  Edm.  Pettier. 
FIG.  13. — Sumerian  Sculpture  with  Eyes  Set  in  Asphalt. 

of  an  animal  in  primitive  form,  hewn  from  a  mass  of  asphalt.    The 
French  chemist,  Henri  Le  Chatelier,  analyzed  some  of  the  jtsphalt, 
and  found  it  to  consist  of  the  fol- 
lowing:15 

Moisture,  2.8  per  cent;  asphalt, 
24.4  per  cent;  wax,  1.6  per  cent; 
mineral  matter,  71.2  per  cent.  The 
mineral  matter  was  composed  of: 
calcium  carbonate,  45.2  per  cent; 
calcium  sulfate,  3.5  per  cent;  cal- 
cium phosphate,  0.8  per  cent;  iron, 
aluminium  and  silicon  oxides,  21.7 
per  cent. 

This  is  conclusive  proof  that 
the  asphalt  is  a  natural  product 

composed  of  25  per  cent  asphalt  and  75  per  cent  mineral  matter, 
similar  to   the   material   obtained   in   the   locality   at  the   present 

day. 

Small  statues  of  Sumerian  origin  (about  2500  B.C.)  have  been 
unearthed  in  Mesopotamia,  composed  of  white  clay  with  wigs  of 
asphalt  and  blobs  of  red  paint  on  the  cheeks.16 

Gudea  of  Lagash  (about  2700  B.C.) .  Another  relic,  known  as 
the  "Libation  Vase"  (Fig.  16)  is  composed  of  green  steatite,  carved 


From   "Memoires   de   la   Delegation 
en   Perse,"  by  Edm.   Pettier. 


pIG. 


4.  —  Persian  Vases  Hewn  from 
Blocks  of  Asphalt. 


14 


HISTORICAL  REVIEW 


in  the  form  of  strange  mythical  monsters,  the  effect  of  which  is 
heightened  by  incrusted  little  shells  set  in  asphalt,  to  represent  the 


From  "Memoires  de  la  Delegation  en  Perse,"  by  Edm.  Pettier. 
FlG.  15. — Primitive  Animal  Carved  from  Asphalt. 

scaly  backs  of  winged  serpents.  The  serpent  was  supposed  to  rep- 
resent the  emblem  of  the  god  Ningish- 
zida,  to  whom  the  accompanying  inscrip- 
tion shows  the  vase  to  be  dedicated  by 
Gudea,  ruler  of  Patesi  of  Lagash.  This 
is  considered  one  of  the  best  specimens 
of  Sumerian  sculpture,  and  represents 
the  height  of  Sumerian  art.  It  is  also 
at  the  Louvre.17 

Another  inscription  credited  to  Gu- 
dea states:18 

From    "The  Civilization  of  Babylonia 

and  Assyria,"  J.  B.  Lippincott  Co.  a*        t      i,     r  A.I_        TV /T        J 

Asphalt  from   the    Magda    moun- 

Fiai6— Libation  Vase  Dedicated  ta}ns    jn    £lam    wag    transported    to    his 

to  Gudea,  Ruler  of  Lagash   (2700  ^.  /•  T  ,    ,,  r 

B.C.),  Showing  Shells  Set  In  As-  <~lty  Ot  JLagash, 
phalt. 

Tablets  of  Gilgamish   (about  2500 

B.C.).  In  the  epic  of  Gilgamish  as  revealed  in  the  twelve  inscribed 
stone  tablets  collected  by  Assur-bani-pal,  king  of  Assyria  (668-626 
B.C.),  we  find  reference  to  the  use  of  asphalt  for  building  purposes. 
These  tablets  date  back  to  about  2500  B.C.  and  constitute  one  of  the 
most  important  pre-Babylonian  literary  records.  In  the  eleventh 
tablet,  Ut-Napishtim  relates  the  wTell-known  story  of  the  Babylonian 
flood,  stating  that  he  usmeared  the  inside  of  a  boat  with  six  sar 
(measures)  of  kupru  (asphalt)  and  the  outside  with  three  sar. 


M19 


I  USE  OF  ASPHALT  BY  PREHISTORIC  RACES  IN  INDIA  15 

The  Persian  writer  al-Kazwini 20  gives  the  following  interesting 
information  relative  to  the  collection  and  treatment  of  asphalt  found 
in  ancient  Persia : 

"There  are  two  kinds  of  native  asphalt.  First  the  kind  that 
oozes  from  certain  mountains;  second  we  have  the  kind  that  appears 
with  water  in  certain  pools.  When  boiled  with  the  water  and  as 
long  as  they  remain  together,  the  asphalt  is  soft;  but  if  we  separate 
them,  the  asphalt  hardens  and  becomes  hard  and  dry.  It  is  col- 
lected by  means  of  matting  and  deposited  on  the  shore.  Then  it  is 
placed  in  a  kettle  under  which  a  fire  has  been  lit,  and  a  certain 
amount  of  sand  is  added  and  a  mix  prepared  by  constant  stirring. 
When  the  mix  is  ready,  it  is  poured  on  the  ground,  where  it  cools 
and  hardens." 

In  ancient  texts  we  are  informed  that  asphalt  mastic  was  always 
sold  by  volume,  namely,  by  the  so-called  "gur,"  the  measure  used 
for  grain,  beer,  etc.,  as  is  evidenced  by  the  very  name  Ur.  Crude 
asphalt,  on  the  other  hand,  was  always  sold  by  weight,  by  the 
"mina"  or  "shekel,"  as  were  metals  and  other  solid  commodities. 

Bur-Sin,  King  of  Ur  (about  2500  B.C.)  An  ancient  Sumerian 
chapel  erected  to  the  Moon  God  "Nin-Gal"  has  recently  been 
excavated,  in  which  the  floors  are  composed  of  burnt  bricks  em- 
bedded in  asphalt  mastic  which  still  shows  impressions  of  reeds  with 
which  it  must  originally  have  been  mixed,  adorned  with  stone 
tablets,  each  of  which  bears  the  following  inscription: 

"Bur-Sin,  King  of  Ur,  of  Sumer  and  Accad,  King  of  the  four 
portions  of  the  World,  has  constructed  this  for  his  Master  Nin-Gal" 

Use  of  Asphalt  by  Pre-historic  Races  in  India  (about  3000 
B.C.).  At  excavations  conducted  in  1923  at  Mohenjo-Daro, 
Harappa  and  Nal,  in  the  Indus  valley,  northwestern  India,  evi- 
dences of  an  advanced  form  of  civilization  have  been  revealed.21 
An  asphalt  mastic,  composed  of  a  mixture  of  asphalt,  clay,  gypsum 
and  organic  matter,  was  introduced  between  two  brick  walls  in  a 
layer  about  i-in.  thick  for  waterproofing  purposes.  A  bathing  pool 
measuring  39  by  23  by  8  feet  in  depth  has  been  unearthed,  located 
in  front  of  an  ancient  temple,  probably  for  ritualistic  cleansing  pur- 
poses, containing  a  layer  of  the  mastic  on  the  outside  of  its  walls  and 
beneath  its  floor,22  as  illustrated  in  Figs.  17  and  18. 


16 


HISTORICAL  REVIEW 


The  mastic  was  found  to  have  the  following  composition: 

Organic  constituents 28.3  per  cent 

Mineral  constituents  71.7  per  cent 


Total    100.0  per  cent 

The  organic  constituents  were  29.3%  soluble  in  carbon  disul-. 
fide  and  85.5%  in  pyridine,  and  contained  7.1%  sulfur.  The 
mineral  constituents  contained:  SiO2  and  insoluble:  55.1%;  Fe2O3 
and  A12O3:  11.296;  CaSO*:  13.7^;  CaO:  4.896;  MgCO3:  4.296; 


Photo   Archeol.    Survey  of  India 
FIG.  17. — Water  Tank  in  Front  of  a  Temple  Excavated  at  Mohenjo  Daro  (Indus  Valley). 

vanadium  and  nickel:  traces.  This  mastic  was  also  used  for 
mosaic  and  inlaid  work,  as  an  adhesive  for  the  application  of  orna- 
ments to  statues,  and  as  a  protective  coating  for  woodwork.  Seep- 
ages of  liquid  asphalt,  as  well  as  rock  asphalt  deposits  exist  today 
in  India,  on  the  Basti  river,  near  Isakhel  (Kashmir)  and  in  the 
Sierras  in  Hazara  District. 

Use  of  Asphalt  by  the  Early  Egyptians  (2500  to  1500  B.C.).23 
The  ancient  Egyptians  were  the  first  to  adopt  the  practice  of  em- 


USE  OF  ASPHALT  BY  THE  EARLY  EGYPTIANS 


17 


balmlng  their  dead  rulers  and  wrapping  the  bodies  in  cloth  which 
was  coated  with  liquid,  or  melted,  solid  waterproofing  substances, 
including  balsams,  oleb-resins,  gum-resins,  true  resins,  wood-tar 
pitch  (obtained  during  the  process  of  charcoal  making),  and  fre- 
quently with  natural  asphalt,  although  Alfred  Lucas,  formerly  di- 
rector of  the  Chemical  Department  of  Egypt,  has  recently  con- 
tended that  he  has  been  unable  to  detect  asphalt  in  the  black 
substance  covering  embalmed  mummies,  and  concludes  that  resin 


Photo  Archeol.    Survey  of  India 
FIG.  18. — Wall  of  Water  Tank  at  Mohenjo  Daro,  Showing  the  Bituminous  Layer. 

employed  for  this  purpose.  Strabo  24  informs  us  that  "the 
Egyptians  used  the  Dead  Sea  asphalt  for  embalming  their  dead," 
and  this  practice  is  also  alluded  to  by  Diodorus  Siculus,  Pliny  the 
Elder,  Dioscorides,  and  other  writers  (loc.  cit).  The  preserved 
remains  are  known  as  "mummies"  (Fig.  19). 

Before  1000  or  900  B.C.  asphalt  was  rarely  used  in  mummifi- 
cation, except  to  coat  the  cloth  wrappings  and  thereby  protect  the 
body  from  the  elements.  After  the  viscera  had  been  removed,  the 
cavities  were  filled  with  a  mixture  of  resins  and  spices,  the  corpse 


18 


HISTORICAL  REVIEW 


immersed  in  a  bath  of  potash  or  soda,  dried,  and  finally  wrapped 
From  500  to  about  40  B.C.  (i.e.  in  Roman  times),  asphalt  was 
generally  used  both  to  fill  the  corpse  cavities,  as  well  as  to  coat  the 
cloth  wrappings.25  The  word  umumia"  first  made  its  appearance 
in  Arabian  and  Byzantine  literature  about  1000  A.D.,26  signifying 
"bitumen."  In  Persian  it  acquired  the  meaning  "paraffin  wax," 
and  in  Syriac  alluded  to  "substances  used  for  mummification." 

The  product  "mumia"  was  used  in  prescriptions,  as  early  as  the 
1 2th  century,  by  the  famous  Arabian  physician  Al  Magor,  for  the 


FIG.  19. — Mummy  Preserved  with  Asphalt 

treatment  of  contusions  and  wounds.  Its  production  soon  became 
a  special  industry  in  the  hands  of  the  Alexandrian  Jews.  As  the 
supply  of  mummies  was  of  course  limited,  other  expedients  came 
into  vogue.  The  corpses  of  slaves  or  criminals  were  filled  with 
asphalt,  swathed  and  artificially  aged  in  the  sun.  This  deception 
continued  for  several  centuries  until  in  1564  A.D.,  it  was  exposed 
after  a  journey  into  Egypt  by  the  French  physician,  Guy  de  la  Fon- 
taine, and  as  a  result,  this  trade  became  extinct  in  the  iyth  century. 
The  earliest  mummies  in  existence  concerning  which  we  have 
authentic  data,  date  back  to  the  Sixth  Egyptian  Dynasty  (about 
2500  B.C.).  The  earliest  specimens  include  the  mummy  of  Seker- 


I  USE  OF  ASPHALT  IN  BIBLICAL  TIMES  19 

em-sa-f,  unearthed  at  Sakkarah  in  1881,  and  exhibited  at  Giza, 
near  Cairo,27  and  the  mummy  of  King  Merenre,  now  at  the  Boulak 
Museum,  Cairo.28 

Tut-ankh-amen  (or  Tutenkhamun),  the  boy  Pharaoh,  who  ruled 
Egypt  about  2000  B.C.  and  whose  treasure-filled  tomb  was  discov- 
ered by  Lord  Carnarvon  of  England  in  1923,  contained  two  statues 
of  the  Pharaoh,  a  black  box,  a  figure  of  a  swan,  a  couch,  an  ancient 
chariot,  and  numerous  other  wooden  objects  preserved  by  impreg- 
nation with  asphalt. 

Use  of  Asphalt  in  Biblical  Times  (2500  to  1500  B.C.).29  Some 
contend  that  Noah  used  asphalt  in  the  construction  of  the  Ark 
(Genesis  VI,  4).  The  Biblical  text  reads,  that  it  was  treated  with 
"pitch"  within  and  without:  "bituminabis  earn  bituminae"  (Vul- 
gate). There  is  little  doubt  but  that  asphalt  was  used  for  this 
purpose,  since  it  is  well  known  that  canoes  and  dugouts  in  the  early 
days  were  made  water-tight  in  the  same  way.  In  fact,  a  number 
of  primitive  tribes  to-day  adopt  the  same  procedure.  If  asphalt 
was  actually  used  by  Noah,  the  date  would  be  fixed  at  approximately 
2500  B.C.,  which  is  usually  assigned  to  the  Deluge. 

We  find  numerous  other  references  in  the  scriptures  to  sub- 
stances corresponding  to  what  we  now  know  to  be  asphalt.  The 
Book  of  Genesis  (XI,  3)  in  describing  the  building  of  the  Tower  of 
Babel  (about  2000  B.C.)  states  ".  .  .  and  they  had  brick  for  stone, 
and  slime  had  they  for  mortar."  There  seems  to  be  no  question 
but  that  the  so-called  "slime"  alludes  to  asphalt,  since  the  word 
translated  as  "slime"  in  the  English  version  (1568),  occurs  as 
d<r<£aXros  in  the  Septuagint,  and  as  "bitumen"  in  the  Vulgate. 

In  the  Septuagint,  or  Greek  version  of  the  Bible,  this  word  is 
translated  as  "asphaltos,"  and  in  the  Vulgate  or  Latin  version,  as 
"bitumen."  In  the  Bishop's  Bible  of  1568  and  in  subsequent  trans- 
lations into  English,  the  word  is  given  as  "slime."  In  the  Douay 
translation  of  1600,  it  is  "bitume,"  while  in  Luther's  German  ver- 
sion, it  appears  as  "Thon,"  the  German  word  for  clay. 

Similarly,  in  Genesis  (XIV,  10)  we  are  informed  that  the  Vale 
of  Siddim  "was  full  of  5/m^pits,"  referring  no  doubt  to  exudations 
of  liquid  asphalt.  Moreover,  it  is  pointed  out  by  certain  authorities 
that  the  area  described  as  the  Vale  of  Siddim  corresponds  to  our 
present  Dead  Sea,  from  which  asphalt  is  still  obtained. 


20 


HISTORICAL  REVIEW 


Again  we  are  told  (Exodus  II,  3)  that  in  constructing  the  basket 
of  bulrushes  in  which  Moses  was  placed,  it  was  daubed  "with  slime 
and  with  pitch"  This  took  place  about  1500  B.C.30  As  was  pointed 
out  previously,  this  constituted  an  early  method  of  constructing 
boats.  Even  at  the  present  time,  boats  known  as  "guffas"  as  illus- 
trated in  Fig.  20  are  constructed  of  woven  reeds  caulked  with  as- 


FIG.  20.— The  Guffa,  or  Coracle,  Used  for  Centuries  in  Parts  of  the  Near  East. 

phalt,31  and  are  used  to  ferry  passengers  and  merchandise  across 
the  Tigris  river  at  Baghdad. 

While  excavating  at  the  ancient  Biblical  city  of  Jericho  in  Pales- 
tine,32 brick  walls  were  found  in  which  asphalt  mastic  was  used  as 
mortar,  dating  back  to  about  2500-2100  B.C. 

It  is  also  contended  that  the  glance  pitch  deposit  known  as  uSuk- 
El-Chan,"  on  the  western  slope  of  Mount  Hermon  in  the  upper 
Jordan  valley,  near  Hasbaya  (loc.  cit.)  has  been  worked  since  about 
1600  B.C. 

Use  of  Asphalt  by  the  Babylonians  (2500  to  538  B.C.).  Baby- 
Ionia  was  the  name  given  to  the  plain  of  the  Tigris  and  Euphrates 


I  USE  OF  ASPHALT  BY  THE  BABYLONIANS  21 

rivers,  now  forming  the  modern  province  of  Irak.  The  Babylonians 
were  well  versed  in  the  art  of  building,  and  each  monarch  commemo- 
rated his  reign  and  perpetuated  his  name  by  constructing  some  vast 
engineering  work.  Certain  kings  built  roadways,  others  built  re- 
taining walls  to  impound  the  waters  of  the  Euphrates,  and  still  others 
mighty  battlements  and  palaces.  Such  facts  were  indelibly  recorded 
by  inscriptions  on  the  bricks  used  for  the  purpose,  many  of  which 
are  still  in  existence.  The  bricks  were  of  the  so-called  "plano- 
convex" type,  being  formed  by  hand,  with  one  side  flat  and  the 
other  face  convex  and  then  kiln  burnt.  Bitumen  was  used  as  mor- 
tar from  very  early  times.  Sand,  gravel  or  clay  were  employed  in 
preparing  these  mastics.  Due  to  the  porous  nature  of  the  bricks, 
the  asphalt  was  partially  absorbed,  resulting  in  a  very  strong  bond. 
At  first,  the  spaces  between  the  bricks  was  filled  with  a  3  to  6  cm. 
layer  of  mastic,  but  in  later  periods  there  was  a  tendency  to  dimin- 
ish the  space. 

Asphalt-coated  tree  trunks,  e.g.  poplar,  were  often  used  to  rein- 
force wall  corners  and  joints,  as  for  instance  in  the  temple  tower  of 
Ninmach  in  Babylon.  In  vaults  or  arches  a  mastic-loam  composition 
was  used  as  mortar  for  the  bricks,  and  the  keystone  was  usually 
dipped  in  asphalt  before  being  set  in  place.  Reuther  reports  that 
bituminous  paint  was  applied  to  the  outer  walls  of  buildings  in 
Babylon  over  a  loam  plaster,  first  primed  with  a  gypsum  distemper. 
Asphalt  was  also  used  to  waterproof  brick  basins  at  Ur  and  Erech.83 

King  Khammurabi  (about  2200  B.C.).  The  use  of  bitumi- 
nous mortar  was  said  to  have  been  introduced  in  the  city  of  Babylon 
by  King  Khammurabi  (Amraphel  of  the  Bible).  Robert  Koldewey 
reports  that  when  excavating  in  Babylon,  he  found  "it  was  exceed- 
ingly difficult  to  separate  the  brick  courses  from  each  other."  34 
This  \vas  also  confirmed  by  A.  H.  Layard,  who  states  that  "Bricks 
bonded  with  asphalt  have  remained  immovably  in  place  for  thou- 
sands of  years."  35 

Queen  S  emir  amis  (about  700  B.C.)  Queen  Semiramis  is 
stated  to  have  built  a  tunnel  under  the  Euphrates  at  Babylon,  about 
1000  meters  long,  of  burnt  bricks  coated  with  asphalt  as  mortar.36 
The  asphalt  thus  functioned  as  a  waterproofing  agent,  very  much 
in  the  same  manner  as  it  is  used  to-day. 

King  Nabopolassar  (625  to  604  B.C.).    Nabopolassar  is  cred- 


22  HISTORICAL  REVIEW  I 

ited  with  having  built  a  palace  on  a  platform  consisting  of  ten 
courses  of  burnt  bricks  set  with  an  asphalt  mortar  and  surfaced 
with  a  layer  of  asphalt  mastic.  One  of  his  inscriptions  states  : 

UI  made  a  Nabalu  and  laid  its  foundations  against  the  bosom  of 
the  underworld,  on  the  surface  of  the  water,  in  bitumen  and  brick. 
I  raised  its  roof  and  connected  the  terrace  with  the  palace.  With 
bitumen  and  brick,  I  made  it  tall  like  unto  wooded  mountains." 

According  to  his  son  Nebuchadnezzer,  he  is  given  the  credit  to 
have  laid  the  first  asphalt  block  pavement  in  Babylon. 

King  Nebuchadnezzar  (604  to  561  B.C.).  Of  all  the  Baby- 
lonian rulers,  Nebuchadnezzar  was  the  most  progressive,  and  is 
stated  to  have  reconstructed  the  entire  city.  The  bricks  bore  in- 
scriptions relating  to  his  work,  and  several  refer  specifically  to  the 
use  of  asphalt.  One  found  in  the  so-called  "Procession  Street" 
(Aiburshabu)  which  led  from  his  palace  to  the  North  wall,  reads  as 
follows : sr 

"Nebuchadnezzar,  King  of  Babylon,  he  who  made  Esaglia  and 
Ezida  glorious,  son  of  Nabopolassar,  King  of  Babylon.  The  streets 
of  Babylon,  the  Procession  Street  of  Nabu  and  Marduk,  my  lords, 
which  Nabopolassar,  King  of  Babylon,  the  father  who  begot  me,  had 
made  a  road  glistening  with  asphalt  and  burnt  bricks;  I,  the  wise 
suppliant  who  fears  their  lordships,  placed  above  the  bitumen  and 
burnt  bricks,  a  mighty  superstructure  of  shining  dust,  made  them 
strong  within  with  bitumen  and  burnt  bricks  as  a  high-lying  road. 
Nabu  and  Marduk,  when  you  traverse  these  streets  in  joy,  may  bene- 
fits for  me  rest  upon  your  lips;  life  for  distant  days,  and  well-being 
for  the  body.  Before  you  I  will  advance  upon  them.  May  I  attain 
eternal  age!" 

This  street  was  constructed  with  stone  slabs  brought  from  distant 
parts,  set  in  a  bituminous  mortar,  the  interstices  being  very  narrow 
at  the  surface  and  widening  towards  the  base  of  the  stones.  The 
foundation  consisted  of  three  or  more  courses  of  bricks  joined  to- 
gether with  bituminous  mortar. 

This  would  seem  to  be  the  forerunner  of  the  present-day  pave- 
ment composed  of  stone  blocks  set  in  asphalt.  It  seems  strange  that 
the  art  should  have  become  lost  to  mankind,  only  to  be  rediscovered 
in  the  nineteenth  century  A.D. 

The  most  comprehensive  relic  left  by  Nebuchadnezzar  is  known 


I  USE  OF  ASPHALT  BY  THE  BABYLONIANS  23 

as  the  "Large  Inscribed  Stone  Tablet"  (sometimes  referred  to  as 
the  "East  India  House  Inscription"),  which  contains  a  detailed  ac- 
count of  his  building  activities.  A  translation  by  Fr.  Delitsch  38 
reads  in  part  as  follows  (Column  7,  lines  34  et  seq.)  : 

"In  Babil,  my  favorite  city  that  I  love,  was  the  palace,  the  house, 
the  marvel  of  mankind,  the  center  of  the  land,  the  dwelling  of 
majesty,  upon  the  Babil  place  in  Babil,  from  Imgur-Bel  to  the  eastern 
canal  Libil-Higalla ;  from  the  bank  of  the  Euphrates  to  Aiburshabu, 
which  Nabopolassar,  King  of  Babylon,  my  father,  my  begetter,  built 
of  crude  bricks,  and  dwelt  in  it  In  consequence  of  high  waters,  its 
foundations  had  become  weak,  and  owing  to  the  filling  up  of  the 
streets  of  Babil,  the  gateway  of  that  palace  had  become  too  low.  I 
tore  down  its  walls  of  dried  brick,  and  laid  its  corner-stone  bare,  and 
reached  the  depth  of  the  waters.  Facing  the  water,  I  laid  its  foun- 
dation firmly,  and  raised  it  mountain  high  with  bitumen  and  burnt 
brick.  Mighty  cedars,  I  caused  to  be  laid  down  at  length  for  its 
roofing.  .  .  .  For  protection,  I  built  two  massive  walls  of  asphalt 
and  brick,  490  ells  beyond  Nimitti-Bel.  Between  them  I  erected  a 
structure  of  bricks  on  which  I  built  my  kingly  dwelling  of  asphalt  and 
bricks.  This  I  surrounded  with  a  massive  wall  of  asphalt  and  burnt 
bricks,  and  made  upon  it  a  lofty  foundation  for  my  royal  dwelling 
of  asphalt  and  burnt  bricks" 

It  thus  appears  that  Nebuchadnezzar  profited  by  the  experience 
of  his  father,  and  instead  of  building  a  retaining  wall  of  dried  clay 
bricks,  which  had  failed  to  hold  back  the  Euphrates  due  to  its  lack 
of  waterproof  properties,  he  resorted  to  the  use  of  burnt  bricks  and 
asphalt,  and  apparently  with  satisfactory  results. 

Robert  Koldewey's  investigations  indicate  that  the  method  of 
constructing  walls  in  Babylonia  and  Nineveh  consisted  in  laying  in 
rotation,  first  a  course  of  bricks,  then  a  layer  of  asphalt,  then  a  layer 
of  clay  and  then  another  course  of  bricks.39  The  joints  in  each 
course  were  composed  of  asphalt  and  clay.  In  every  fifth  course,  the 
clay  was  replaced  by  a  matting  of  reeds.  This  matting  is  now  en- 
tirely rotted  and  gone,  but  its  impression  is  clearly  recognizable  in 
the  asphalt.  An  attempt  to  separate  the  courses  to  prevent  adhesion 
is  thus  apparent,  but  the  reason  is  not  obvious.  Only  in  one  locality 
(Temple  of  Borsippa)  does  it  appear  that  asphalt  has  been  used  in 
direct  contact  with  the  bricks,  where  they  still  hold  together  in  a 
firm  mass. 


24 


HISTORICAL  REVIEW 


It  is  probable  that  the  asphalt  used  by  the  Babylonians  was  de- 
rived from  springs  similar  to  the  ones  still  found  in  Mesopotamia, 
of  which  Fig.  21  is  a  typical  example  of  an  asphalt  spring  at  Hit. 
Deposits  of  pure  asphalt  are  found  to-day  at  various  localities  in 
this  region,  including  Ain  Mamurah,  Ain-el-Maraj,  Al-Kuwait 
(Arabia),  Bushire  (Iran),  and  Bundar  Abbas  (Iran). 

Figure  22  shows  the  present  appearance  of  the  brick  floor  of 
Nebuchadnezzar's  Throne  Hall,  Babylon,  looking  towards  the 


From  "Light  on  the  Old  Testament,"  by  Prof.  A.  T.  Clay. 
FIG.  21. — Asphalt  Spring  in  Mesopotamia. 

Euphrates.  The  burnt  bricks  bearing  the  name  of  Nebuchadnezzar 
(of  which  one  is  shown  in  the  foreground)  were  laid  in  asphalt,  and 
are  still  so  firmly  jointed  together  to-day,  that  it  is  impossible  to 
part  them  without  destroying  their  integrity.40 

King  Nebuchadnezzar  also  built  a  bridge  across  the  Euphrates 
near  Babylon,  370  feet  long.  The  piers  were  constructed  of  burnt 
bricks  embedded  in  asphalt  mastic,  the  bases  of  which  were  pro- 
tected with  a  superficial  coating  of  asphalt.  He  also  constructed 
large  sewers  ("cloacae")  for  draining  the  city  of  Babylon,  lined 
with  blocks  composed  of  a  mixture  of  asphalt,  loam  and  gravel. 


I 


USE  OF  ASPHALT  BY  THE  ASSYRIANS 


25 


The  use  of  bituminous  mortar  was  abandoned  in  Babylon 
towards  the  end  of  Nebuchadnezzar's  reign,  in  favor  of  lime  mor- 
tar to  which  varying  amounts  of  asphalt  were  added.  After  the 
fall  of  Babylon  (538  B.C.)  even  the  addition  of  asphalt  was  dis- 
continued. In  the  ensuing  Persian  period  (538  to  300  B.C.),  the 


Copyright  by  Underwood  &  Underwood,  N.  Y. 


FIG.   22. — Floor  of  Nebuchadnezzar's  Temple  as  it  Appears  To-day,   Showing  Blocks 

Joined  by  Means  of  Asphalt. 

lime  was  replaced  in  turn  writh  clay  as  mortar,  and  this  resulted  in  a 
retrogression  in  the  building  art. 

Use  of  Asphalt  by  the  Assyrians  (1400  to  607  B.C.).41  The 
name  Assyria  was  derived  from  the  city  of  Assur  (now  Kalah 
Shargat)  situated  on  the  right  bank  of  the  Tigris,  midway  between 
the  Greater  and  Lesser  Zab  rivers.  Assur  was  finally  supplanted 


26  HISTORICAL  REVIEW  I 

by  Nineveh  as  capital  (Nebi  Yanus  and  Kuyunjik)  some  60  miles 
farther  north. 

King  Adad-Nirari  I  (about  1300  B.C.).  This  monarch  is  stated 
to  have  built  an  embankment  i  mile  long  along  the  banks  of  the 
Tigris,  in  which  the  stones  were  joined  together  with  an  asphaltic 
mortar.  W.  Andrae  reports  that  tablets  have  been  found  in  the 
embankment  at  Assur,  recording  the  fact  that  the  asphalt  ("kupru"  : 
pitch)  used  was  mined  at  Ubase  (present  Quala  Shargat),  and  in 
reference  to  the  mortar  states  that  "After  3300  years,  it  still  faith- 
fully fulfils  its  purpose."  42  Andrae  likewise  refers  to  an  ancient 
temple  mound  excavated  at  the  former  site  of  Erech,  dating  back 
to  this  same  period,  which  was  constructed  of  courses  of  dried  clay 
bricks  bound  together  with  a  mortar  composed  of  asphalt  mixed 
with  clay.  It  is  interesting  to  note  in  passing,  that  in  the  ancient 
Assyrian  moral  code  we  find  reference  to  asphalt,  which  was  pre- 
scribed to  be  poured  onto  the  heads  of  delinquents  in  a  molten 
state. 

King  Tukulti-Ninurta  11  (890  to  884  B.C.).  This  King,  in  his 
annals  makes  reference  to  the  fact: 43 

"In  front  of  Hit,  by  the  bitumen  springs — the  place  of  Usmeta 
Stones  where  the  gods  speak — I  spent  the  night." 

King  Sargon  (722  to  705  B.C.).  The  following  inscription  oc- 
•curs  on  the  bricks  of  the  so-called  "Sargon  Wall"  of  Babylon,  built 
by  King  Sargon,  founder  of  the  last  and  most  illustrious  Assyrian 
dynasty,  as  it  has  been  translated  by  Fr.  Delitsch : 44 

"To  Marduk,  the  Great  Lord,  the  divine  Creator,  who  inhabits 
Esagila,  the  Lord  of  Babil,  his  lord  Sargon,  the  mighty  king,  King 
of  the  land  of  Assur,  King  of  all,  governor  of  Babil,  King  of  Sumer 
and  Akkad,  the  nourisher  of  Esagila  and  Ezida.  To  build  Imurg- 
Bel  was  his  desire;  he  caused  burnt  brick  of  pure  JKiru  (?)  to  be 
struck,  built  a  kar  (  ?)  with  tar  and  asphalt  on  the  side  of  the  Ishtar 
Gate  to  the  bank  of  the  Euphrates  in  the  depth  of  the  water,  and 
founded  Imgur-Bel  and  Nimitti-Bel  mountain  high,  firm  upon  it. 
This  work  may  Marduk,  the  great  Lord,  graciously  behold,  and 
grant  Sargon,  the  prince  who  cherishes  him,  life!  Like  the  foun- 
dation stone  of  the  Sacred  City,  may  the  years  of  his  reign  endure. " 

"Imgur-Bel"  was  the  name  given  to  the  inner  wall  of  Babylon, 
and  "Nimitti-Ber  to  the  outer.  ^ 


I  REFERENCES  BY  GREEK  AND  ROMAN  WRITERS  27 

King  Sennacherib  (704  to  682  B.C.).  One  of  this  King's  in- 
scriptions 45  informs  us  that  he : 

"Covered  the  bed  of  the  diverted  river  Telbiti  with  rush  matting 
at  the  bottom  and  quarried  stone  on  top,  cemented  together  with 
natural  pitch  (asphalt).  I  thus  had  a  stretch  of  land  454  ells  long 
and  289  ells  wide,  raised  out  of  the  water  and  changed  into  dry 
land"  (Inscription  No.  6). 

The  year  607  B.C.  marked  the  destruction  of  Nineveh  and  the 
end  of  the  Assyrian  empire. 

Use  of  Asphalt  in  Constructing  Lake-Dwellings  (about  1000 
B.C.).  In  the  bronze-age,  dwellings  were  constructed  on  piles  in 
lakes  close  to  the  shore  the  better  to  protect  the  inhabitants  from 
the  ravages  of  wild  animals  and  attacks  from  marauders.  Excava- 
tions have  shown  that  the  wooden  piles  were  preserved  from  decay 
by  coating  with  asphalt.  Remains  preserved  in  this  manner  have 
been  found  in  Switzerland,  in  the  lakes  of  Bourget,  Geneva,  N^u- 
chatel,  Bienne,  Zurich  and  Constance.46 

References  to   Bituminous   Substances   by   Greek   and   Roman 
Writers  (500  B.C.  to  817  A.D.) 

Herodotus  (484  to  425  B.C.).  The  Greek  historian  Herodo- 
tus, in  his  treatise  "Historiarum"  47  refers  to  deposits  of  asphalt  at 
Hit  (the  present  town  of  Kirkuk  in  Mesopotamia)  as  follows: 

"There  is  a  city  called  Is  (Hit),  eight  days'  journey  from  Baby- 
lon, where  a  little  river  flows,  also  named  Is,  a  tributary  stream  of 
the  river  Euphrates.  From  the  source  of  this  river  many  'gouts' 
of  asphalt  rise  with  the  water;  and  from  thence  the  asphalt  is 
brought  for  the  walls  of  Babylon." 

Many  references  occur  in  the  earliest  writings  to  Hit  (Accadian 
"Id,"  Greek  "Is").  A  more  recent  though  interesting  description 
of  the  asphalt  deposit  at  Hit  is  furnished  by  a  British  traveler 
George  Rawlinson  ( I745),48  who  described  his  visit  to  that  locality 
as  follows: 

"Having  spent  three  days  or  better  among  the  ruins  of  old 
Babylon,  we  came  into  a  town  called  Hit,  inhabited  only  by  Arabians, 
but  very  ruinous.  Near  unto  this  town  is  a  valley  of  pitch,  very 
marvelous  to  behold,  and  a  thing  almost  incredible,  wherein  are 
many  springs  throwing  out  abundantly  a  kind  of  black  substance, 


28  HISTORICAL  REVIEW  I 

like  unto  tar  and  pitch,  which  serveth  all  the  countries  thereabouts 
to  make  staunch  their  barks  and  boats.  Every  one  of  which  springs 
maketh  a  noise  like  a  smith's  forge  in  puffing  out  the  matter,  which 
never  ceaseth  night  or  day,  and  the  noise  is  heard  a  mile  off,  swal- 
lowing all  the  weighty  things  that  come  upon  it.  The  Moors  call  it 
the  Mouth  of  Hell." 

A  translation  of  a  tablet  unearthed  at  Karnak49  reveals  the 
fact  that  part  of  the  tribute  paid  Thothmes  III  (Tethmosis  III), 
about  1500  B.C.  from  Mesopotamian  cities  consisted  of  2040  minae 
(about  1000  kg.)  of  "zift"  (Arabic  for  native  asphalt),  sent  by 
the  ruler  of  Is  (Hit),50  but  the  foregoing  has  been  controverted. 

Herodotus  also  states  (VI,  119)  that  asphalt  was  obtained 
from  wells  near  Ardericca  (near  the  present  town  of  Kirab)  in  the 
land  of  Cissia  (now  Persia)  : 

"At  Ardericca,  210  stadia  from  Susa,  there  is  a  well  another 
40  stadia  away,  which  produces  three  different  substances,  since 
asphalt,  salt  and  oil  are  drawn  up  from  it.  ...  It  assumes  three 
different  forms :  the  asphalt  and  the  salt  immediately  become  solid, 
but  the  oil  they  collect,  and  the  Persians  call  it  Rhadinance;  it  is 
black  and  emits  a  strong  odor." 

At  Elam,  in  the  province  of  Susiana  in  Persia,  asphalt  is  still 
collected  in  this  crude  manner. 

Herodotus  refers  (IV,  195)  to  a  deposit  of  pure,  soft  asphalt 
at  Zacynthus  (now  Zante),  on  the  Greek  coast,  as  follows: 

"I  myself  have  seen  the  pitch  drawn  up  out  a  pool  of  water  in 
Zacynthus,  and  there  are  several  pools  there,  the  largest  of  which 
is  70  orgyoe  (i-e-  fathoms)  long  and  broad,  and  2  orgyoe  in  depth. 
Into  this,  they  let  down  a  pole  with  a  myrtle  branch  fastened  to  its 
end,  and  then  draw  up  the  pitch  adhering  to  the  myrtle.  It  has  the 
smell  of  asphalt,  but  in  other  respects  is  better  than  the  pitch  of 
Pieria  (now  Thessalonica).  Then  they  pour  it  into  a  pit  that  has 
been  dug  near  the  pool;  and  when  much  is  collected,  they  fill  their 
vessels  from  the  pit." 

Herodotus  was  the  first  writer  to  describe  the  construction  of 
small  round  boats  woven  together  of  reeds,  like  baskets,  covered  on 
the  outside  with  hides,  and  waterproofed  with  a  coating  of  natural 
asphalt,  similar  to  the  present-day  "guffas"  found  in  Mesopotamia 
(I,  194).  He  also  described  the  use  of  bituminous  mortar,  com- 


I  REFERENCES  BY  GREEK  AND  ROMAN  WRITERS  29 

posed  of  asphalt  and  straw,  for  joining  together  stones  and  clay 
bricks  in  building  masonry  walls  at  Media. 

Thucydides  (471  to  401  B.C.).  The  Greek  hsitorian  Thu- 
cydides  51  refers  to  the  use  of  petroleum  for  military  purposes  and 
describes  a  mixture  of  asphalt  and  sulfur,  which  was  used  to  ignite 
fascines  piled  against  the  wooden  walls  in  the  sieges  of  Plataea 
and  Delium. 

Hippocrates  (460  to  377  B.C.).  This  Greek  philosopher  and 
physician  52  refers  to  several  of  the  asphalt  deposits  already  men- 
tioned. 

Xenophon  (430  to  357  B.C.).  The  Greek  historian  Xeno- 
phon  53  describes  a  wall  built  in  Media,  composed  of  burnt  bricks 
cemented  together  with  asphalt,  similar  to  the  method  of  construc- 
tion used  in  Babylon. 

Aristotle  (384  to  322  B.C.).  This  Greek  writer  and  philoso- 
pher 54  states  : 

''Inflammable  oils  rise  in  large  quantities  in  the  soil  of  Persia, 
and  in  smaller  quantities  in  Sicily,  where  they  often  have  the  distinct 
odor  of  cedar  resin.  Thick,  dark  and  viscous  oils  flow  beside  nat- 
ural pitch  and  asphalt  in  Macedonia,  Thrace  and  Illyria  (Selenitza 
in  Albania)  from  the  hot,  often  burning  soil,  smelling  of  sulfur  and 
bitumen,  and  diffuse  stinking,  choking  and  sometimes  deadly  fumes. " 

Theophrastus  (372  to  288  B.C.).  This  Greek  writer55  de- 
scribes the  production  of  wood  tar,  which  he  states  was  an  estab- 
lished industry.  He  likewise  gives  a  comprehensive  account  of 
several  occurrences  of  asphalt,  and  refers  to: 

"An  earth  in  Cilicia  (present  Turkey-in-Asia ) ,  which  becomes 
viscous  on  heating." 

Antigonus  (about  311  B.C.).  We  are  informed66  that  Antig- 
onus  of  Macedonia  in  311  B.C.  sent  Hieronymus  of  Cardia  with 
an  army  to  capture  the  asphalt  works  at  the  Dead  Sea  from  the 
Nabataeans.  This  deposit  seems  to  have  been  greatly  prized. 
Later,  Ptolemy  II  (309-246  B.C.)  in  turn,  captured  the  Dead  Sea 
asphalt  works.  It  then  passed  on  to  the  Seleucids,  from  whom 
Antony  took  it  and  presented  it  to  Cleopatra.  The  latter  leased  it 
to  Malchus,  the  Nabataean,  in  36  B.C.,  who  in  32-31  B.C.  failed  to 


30  HISTORICAL  REVIEW  I 

pay  rent  and  was  accordingly  punished  by  Herod.    The  subsequent 
history  of  this  most  interesting  deposit  is  lost  in  obscurity. 

Hannibal  (247  to  183  B.C.).  The  Carthaginian  general  Han- 
nibal is  said  to  have  used  asphalt  in  compounding  the  so-called  Greek 
Fire  (ulgnae  Vestoe"),  which  was  claimed  to  burn  so  fiercely,  that 
even  water  would  not  extinguish  it,  and  was  used  extensively  by  him 
in  warfare. 

Vergil  (70  to  19  B.C.).  This  Roman  poet57  refers  to  the  me- 
dicinal use  of  bitumen,  applied  externally  as  a  cure  for  scabies. 

Strabo  (63  B.C.  to  24  A.D.}.  The  Greek  geographer  Strabo  58 
refers  in  detail  to  the  Dead  Sea  asphalt  deposit  This  was  termed 
uLacus  Asphaltites"  by  the  classical  writers,  and  the  asphalt  derived 
therefrom,  as  "Bitumen  Judaicum."  Strabo  states  (XVI,  740)  : 

"The  Dead  Sea  is  full  of  asphalt.  It  comes  to  the  surface  ir- 
regularly at  the  center,  with  noisy  disturbance  of  the  water,  which 
appears  as  though  it  were  boiling.  The  visible  portion  of  the 
asphalt  lumps  is  round  and  has  the  form  of  a  hillock.  Much  sooty 
matter  accompanies  the  gaseous  emanation,  which  tarnishes  copper, 
silver  and  all  bright  metals,  and  even  causes  gold  to  rust." 

He  adds  further  (XVI,  764)  : 

"The  asphalt  remains  on  the  surface  of  the  water,  owing  to  its 
salty  nature.  People  go  in  rafts  to  the  asphalt,  hack  it  to  pieces, 
and  take  as  much  of  it  away  with  them  as  they  can." 

He  also  offers  the  following  interesting  theory  regarding  the 
origin  and  formation  of  Dead  Sea  asphalt  (XVI,  763)  : 

"Asphalt  is  a  lumpy  earth,  which  has  been  liquefied  by  heat  and 
again  comes  forth  and  spreads  out,  and  eventually  becomes  con- 
verted into  a  dense,  solid  mass  by  the  cold  sea  water,  so  that  it 
must  be  worked  with  knives  and  axes.  Undoubtedly,  this  occurs  in 
the  center  of  the  lake,  since  the  fire  originates  there  and  likewise 
the  asphalt.  The  asphalt  is  generated  irregularly,  since  the  move- 
ment of  the  fire,  the  force  of  the  wind,  etc.,  have  no  marked  regu- 
larity." 

Strabo  has  the  following  to  offer  regarding  Babylonian  asphalt 
(I,  16): 

"Poseidonius  (died  51  B.C.)  declares  that  there  are  wells  of 
black  and  also  white  naphtha  in  Babylonia.  The  white  naphtha, 


I  REFERENCES  BY  GREEK  AND  ROMAN  WRITERS  31 

which  attracts  fire,  is  composed  of  liquid  sulfur  (?);  the  black 
naphtha  is  simply  liquid  black  asphalt,  which  can  be  burnt  in  lamps 
instead  of  olive  oil." 

He  states  further  (XVI,  743): 

'There  is  much  asphalt  in  Babylonia,  about  which  Erathosthenes 
(of  Alexandria,  276  to  194  B.C.)  has  the  following  to  say:  "The 
liquid,  which  is  called  naphtha,  is  found  in  the  region  around  Susa. 
The  more  solid  material,  which  may  become  hard,  occurs  in  Baby- 
lonia. The  source  is  near  the  Euphrates.  When  this  river  over- 
flows its  banks,  through  the  melting  of  the  snow  on  the  mountains, 
this  well  also  overflows  and  wends  its  way  to  the  river.  With  it 
come  large  lumps  of  asphalt  which  is  very  suitable  for  use  in  Cement- 
ing bricks  for  house  building.  Others  say  that  the  liquid  kind  also 
occurs  in  Babylonia.  I  have  already  said  how  useful  the  solid  kind 
is  for  the  building  of  houses.  It  is  said  that  ships  are  also  made  of 
it  and  that  if  they  are  coated  with  it,  they  will  become  watertight'." 

Strabo  refers  (XVI,  738)  to  the  use  of  asphalt  mortar,  both 
for  constructing  walls  of  houses  and  for  waterproofing  tunnels.  He 
observes  (VII,  316)  : 

"Asphalt  from  Rhodes  requires  more  olive  oil  for  cutting,  than 
that  from  Pieria  (Thessalonica)." 

He  informs  us  that  "pissasphaltos"  [derived  from  the  Greek 
words  "pissa"  (pix  or  pitch)  and  "asphaltos"  (asphalt)]  59  occurs 
in  the  neighborhood  of  Epidamnos  (or  Dirrachion)  on  the  main- 
land of  Albania,  stating  (VII,  316)  : 

"In  the  country  of  the  Apolloniates  at  a  place  called  Nymph- 
aeum,  there  occurs  a  rock,  at  the  base  of  which,  fire  gushes  forth, 
accompanied  by  streams  of  hot  water  and  melted  asphalt,  and  un- 
doubtedly it  is  the  mass  of  asphalt  that  burns.  This  occurrence  is 
found  near  the  summit.  The  mass  carried  away  by  the  water  is 
eventually  recovered,  since  it  is  again  converted  into  asphalt,  which 
as  Poseidonius  has  noted,  may  be  dug  out  of  the  earth  on  a  hill  in 
the  vicinity." 

This  most  likely  alludes  to  the  present-day  deposit  of  Selenitzia 
in  Albania. 

Strabo  also  refers  to  the  use  of  asphalt  paints,  in  respect  to 
which  he  comments  (XVI,  739)  : 

"For  want  of  wood  for  building,  only  the  beams  and  stays  in 
houses  are  made  of  the  wood  of  the  date-palm.  The  stays  are  stif- 


32  HISTORICAL  REVIEW  I 

fener  with  cord  made  of  plaited  rushes.    Then  everything  is  plas- 
tered and  painted  and  the  doors  are  coated  with  asphalt." 

Diodorus  Siculus  (about  50  A.D.}.  This  Greek  historian60 
also  describes  the  Dead  Sea  deposit  (XIX,  t.  98,  Chap.  2)  as 
follows  : 

" It  is  a  large  sea  which  yields  up  much  asphalt  and  from  which 
a  by  no  means  negligible  revenue  is  derived.  The  sea  is  about  500 
stadia  in  length  and  60  stadia  wide.  The  water  stinks  and  is  exceed- 
ingly bitter,  so  that  fish  cannot  live  in  it,  nor  do  any  other  creatures 
occur  in  it.  Although  large  rivers  of  very  fresh  water  flow  into  it, 
the  sea  remains  bitter.  Every  year  a  large  quantity  of  asphalt  in 
pieces  more  than  3  plethra  (no  yards)  float  in  the  middle  of  the 
sea.  The  advent  of  asphalt  is  heralded  20  days  before  its  arrival, 
for  all  around  the  sea  the  stench  is  wafted  by  the  wind  over  many 
stadia,  and  all  the  silver,  gold  and  copper  in  the  neighborhood  be- 
come tarnished,  but  the  tarnish  disappears  again  when  the  asphalt 
rises  to  the  surface.  The  district  in  the  vicinity,  which  is  readily 
inflammable,  and  which  is  pervaded  by  an  unpleasant  odor,  makes 
the  people's  bodies  ill  and  they  die  young."  61 

In  connection  with  the  Babylonian  asphalt  deposits,  he  states 
(II,  Chap.  12): 

uOf  all  the  many  wonders  occurring  in  Babylonia  the  most 
astounding  consists  of  the  large  deposits  of  asphalt  which  are  found 
there.  So  much  is  found  that  it  not  only  suffices  for  many  and  large 
buildings,  but  the  surplus  is  used  by  the  populace,  who  gather  large 
quantities  in  various  localities,  which  after  drying  is  used  as  fuel  in 
place  of  wood.  In  spite  of  the  large  number  of  inhabitants  who  thus 
consume  the  asphalt,  its  supply  remains  as  inexhaustible  as  the  water 
from  the  wells. 

He  also  alludes  to  the  fact  that  in  constructing  the  walls  of  the 
city  of  Media,  the  stones  were  cemented  together  with  an  asphalt 
mortar,  as  previously  remarked  by  Herodotus  and  Xenophon.  He 
refers  to  the  use  of  asphalt  for  embalming  the  dead  (XIX,  t.  98, 
Chap.  2),  stating: 

"The  largest  portion  of  the  asphalt  derived  from  the  Dead  Sea 
is  exported  to  Egypt,  where  among  other  uses,  it  is  employed  to 
mummify  dead  bodies,  for  without  the  mixture  of  this  substance 
with  other  aromatics,  it  would  be  difficult  for  them  to  preserve  these 
for  a  long  time  from  the  corruption  to  which  they  are  liable." 


I  REFERENCES  BY  GREEK  AND  ROMAN  WRITERS  33 

Vitruvms  (about  50  A.D.}.  The  Roman  architect  Vitruvius, 
otherwise  known  as  Marcus  Vitruvius  Pollio  62  refers  to  the  pres- 
ence of  asphalt  in  the  neighborhood  of  Babylon,  which  he  describes 
as  being  of  a  liquid  consistency,  and  states  further  (VII,  3  and  8)  : 

uAsphalt  is  found  in  Carthage  and  Ethiopia,  and  fluid  and  solid 
varieties  are  found  in  Arabia  .  .  .  likewise  near  Joppa  in  Syria. 
...  In  nomad  Arabia  are  lakes  of  immense  size  producing  much 
bitumen  which  is  gathered  by  the  neighboring  tribes.  This  is  not 
surprising,  because  there  are  many  quarries  of  hard  bitumen  there. 
When  a  spring  of  water  flows  through  this  land,  it  draws  the  bitu- 
men with  it,  and  passing  along,  the  water  disappears  and  deposits 
the  bitumen." 

He  likewise  refers  (I,  5  and  8)  to  the  Dead  Sea  occurrence, 
those  at  the  city  of  Hit,  also  to  the  Albanian  deposit,  and  mentions 
the  use  of  asphalt  mortar  for  constructing  masonry  walls  at 
Media. 

Pliny  the  Elder  (23  to  79  A.D.}.  This  Roman  naturalist63 
refers  to  Dead  Sea  asphalt  (XXXV,  178)  as  uslimy  bitumen"  and 
states  that  a  deposit  is  found  in  solid  form  "as  an  earth"  in  the  vi- 
cinity of  Sidon,  which  undoubtedly  corresponds  to  the  present  Suk- 
el-Chan  glance  pitch  mine  (loc.  cit. ).  Pliny  refers  (VI,  99)  to 
another  deposit,  most  likely  in  the  neighborhood  of  the  present  town 
of  Bushire  in  Mesopotamia,  stating: 

"Here  flows  the  river  Granis  through  Susiana,  on  the  right  bank 
of  which  the  Deximontani  dwell,  who  manipulate  bitumen." 

Again,  he  refers  (II,  235)  to: 

"Petroleum  wells  at  Astacensis  in  Parthia  (northeastern  Persia) 
capable  of  yielding  asphalt." 

Pliny  describes  (XXXV,  178)  how  the  natives  of  Sicily  gather 
asphalt,  as  follows: 

"The  inhabitants  gather  the  asphalt  from  the  surface  of  pools, 
by  stirring  with  branches,  to  which  it  will  easily  adhere." 

He  comments  (VII,  65 )  upon  the  high  ductility  of  good  asphalt: 

"Asphalt  that  is  elastic  and  cohesive  cannot  be  split  apart,  since 
it  adheres  to  all  objects  that  come  in  contact  with  it.  It  will  draw 
out  into  long  threads  when  anything  is  dipped  into  the  sticky  mass," 


34  HISTORICAL  REVIEW  I 

Again  (XXXV,  180): 

"Bitumen  is  prized  most  highly  when  it  is  bright  and  heavy; 
and  becomes  less  bright  when  mixed  with  pitch.  It  has  the  same 
properties  as  sulfur;  it  cracks,  but  heals  itself,  since  the  cracks  again 

close  up." 

•*   * 

He  states  further  that: 

"The  best  quality  floats  on  the  surface  when  the  mass  is^  boiled 
.  .  .  and  liquid  bitumen  is  burnt  in  lamps  in  place  of  olive  oil" 

Pliny  alludes  to  "pissasphaltos"  (XXIV,  41;  XXXV,  182)' as 
follows : 

"A  mixture  of  pitch  and  asphalt  being  termed  pissasphaltos.1' 

He  refers  to  "ampelitis,"  i.e.  mineral  wax  (XXXIV,  194)) 
stating : 

"Ampelitis  greatly  resembles  bitumen,  and  like  bitumen  becomes 
liquid  when  it  has  absorbed  oil." 

He  further  informs  us  that  "gagates"  (asphaltite  or  jet)  are 
found  in  Lycia  (XXXVI,  141). 

Pliny  refers  to  the  production  of  wood  tar  (XIV,  122  and  127; 
XVI,  38  and  52)  as  follows: 

"Stacking  a  large  pile  of  wood,  covering  it  with  a  layer  of  earth 
or  sods  and  then  setting  fire  to  the  wood.  The  tar  produced  in  this 
manner  is  drawn  off  through  a  drain  16  ells  long  leading  from  under 
the  stack." 

He  also  alludes  to  the  production  of  wood-tar  pitch  (XVI,  52) 
as  follows: 

"The  boiling  of  pitch  (Latin:  'picem  coquere'  )  derived  from 
wood  tar." 

Likewise,  that  (XV,  8;  XXIV,  24)  : 

"Tar  oil  can  be  obtained  by  stretching  a  hide  over  a  cauldron 
containing  boiling  pitch,  and  then  wringing  out  the  condensed  liquid." 

He  refers  to  the  use  of  wood  tar  and  wood-tar  pitch  for  water- 
proofing pottery  (XIV,  134;  XV,  62),  for  calking  ships  (XVI,  56 
and  158),  and  as  a  paint  for  roofs  and  walls  (XXXV,  41; 
XXXVI,  1 66). 


I  REFERENCES  BY  GREEK  AND  ROMAN  WRITERS  35 

Pliny  refers  to  the  use  of  asphalt  in  warfare  as  follows  (CIV)  : 

uThe  attack  of  Lucullus  on  the  city  of  Samosata  was  repelled 
with  the  assistance  of  burning  maltha.  ...  In  the  city  of  Samosata 
in  Commagene,  there  is  a  body  of  water  on  the  surface  of  which 
there  was  ignited  a  mass  of  slime  called  maltha.  When  this  slime 
comes  in  contact  with  any  solid  bodies,  it  adheres  to  them  and  fol- 
lows those  that  retreat  Thus  as  the  city  was  besieged  by  Lucullus, 
the  inhabitants  ignited  the  walls  and  drove  back  the  soldiers  and 
destroyed  their  weapons.  Experiments  have  proven  that  the  burn- 
ing slime  can  only  be  extinguished  with  damp  earth." 

He  comments  (XXXIV,  15)  on  the  use  of  asphalt  as  a  paint: 

"The  ancients  coated. their  bronze  monuments  wjth  bitumen, 
which  makes  it  all  the  more  remarkable  to  remember  that  they  pre- 
ferred to  cover  them  with  gold.  I  do  not  know  whether  it  is  a 
Roman  invention,  although  it  is  said  that  it  was  done  at  Rome  first." 

And  again  (XXXV,  183): 

"Copper  house  utensils  are  painted  with  bitumen  to  make  them 
more  resistant  to  heat  and  flame.  .  .  .  Iron  workers  use  it  in  their 
workshops  for  varnishing  iron,  for  the  heads  of  nails,  and  for  many 
other  purposes." 

He  also  refers  (XIV,  20)  to  the  use  of  asphalt: 

"To  coat  the  inside  of  wine  casks  and  water  receptacles." 

Pliny  describes  the  use  of  asphalt  for  medicinal  purposes 
(XXXV,  1 80  and  182)  and  recommends  it  for  curing  boils,  inflam- 
mation of  the  eyes,  coughs,  asthma,  blindness,  epilepsy,  etc.  He  tells 
us  that  it  was  sold  under  the  name  mumia,  which  we  are  informed 
was  actually  scraped  from  the  mummies  taken  from  tombs.  Its 
alleged  curative  properties  wrere  explained  by  the  fact  that  it  pre- 
served the  dead  for  so  many  centuries.64 

Josephus  Flavins  (37  to  95  A.D.}.  This  Roman  historian66 
referred  to  Dead  Sea  asphalt  stating: 

"The  changes  in  the  color  of  the  Dead  Sea  are  astonishing,  since 
it  alters  three  times  daily  and  when  the  sun's  rays  change  their  direc- 
tion they  are  reflected  irregularly." 

He  also  describes  the  use  of  bitumen  in  medicine  as  a  remedy 
for  trachoma,  leprosy,  gout  and  eczema. 

Plutarch  (about  46  A.D.}.  This  Greek  historian  Plutarch66 
informs  us : 


36  HISTORICAL  REVIEW  I 

UA  Macedonian  named  Proxenus,  who  had  charge  of  the  King's 
equipage,  on  opening  the  ground  by  the  river  Oxus  (present  Turko- 
man Republic)  in  order  to  pitch  his  master's  tent,  discovered  a  spring 
of  gross  oily  liquor,  which  after  the  surface  was  taken  off  came 
perfectly  clear  and  neither  in  taste  nor  smell  differed  from  olive  oil, 
nor  was  it  inferior  to  it  in  smoothness  and  brightness,  though  there 
was  no  olive  tree  in  that  country.  It  is  said  indeed,  that  the  water 
of  the  Oxus  is  of  so  unctuous  a  quality,  that  it  makes  the  skin  of 
those  who  bathe  in  it  smooth  and  shining." 

Tacitus  (55  to  117  A.D.}.  The  Roman  historian  states67  in 
reference  to  Dead  Sea  asphalt: 

"Those  whose  calling  is  to  gather  asphalt,  draw  one  end  into 
their  boat,  whereupon  the  balance  of  the  mass  will  follow  without 
effort.  This  is  continued  until  the  vessel  is  filled,  whereupon  the 
viscous  mass  is  cut  to  pieces.  .  .  .  This  unusual  substance  floats 
in  heaps  upon  the  Dead  Sea  and  is  either  towed  or  pulled  ashore 
by  hand,  where  it  is  easily  manipulated.  When  it  is  sufficiently 
dried,  either  by  the  heat  of  the  sun  or  by  the  vapors  of  the  earth,  it 
becomes  hard  and  may  be  broken  up  into  pieces,  as  wood  or  stone, 
by  means  of  chisels  or  the  force  of  axes.  .  .  .  The  hardening  may 
be  hastened  by  wetting  with  vinegar  until  it  acquires  the  desired 
cohesion." 


Aelian  (Aelianus  Claudius]  —  (about  laoA.D.).  This  Roman 
writer  and  rhetorician  refers  to  various  sources  of  asphalt68 

Dioscorides  (about  150  A.D.).  The  Greek  physician  Dioscori- 
des69  states  (I,  83)  that  there  is  a  source  of  asphalt,  referred  to 
by  him  as  "Lacus  Asphaltites,"  at  Sidon,  which  is  assumed  to  refer 
to  Siddim,  i.e.,  to  the  Dead  Sea  deposit.  He  states  further  that: 

"Asphalt  is  found  in  its  liquid  state  at  Acragantium  (the  present 
Agrigento)  in  Sicily.  It  floats  on  the  surface  of  the  springs.  It 
is  a  kind  of  liquid  bitumen  and  is  used  in  lamps  in  place  of  olive  oil." 

He  also  alludes  to  Albanian  asphalt  under  the  term  "pissasphal- 
tos"  as  follows  (I,  84)  : 

"In  the  vicinity  of  Epidamnos  (i.e.  Dirrachion  in  Albania), 
there  is  found  a  substance  called  'pissasphaltos.'  It  comes  down 
from  the  Ceraunic  mountains  and  is  carried  along  by  the  force  of 
the  water  and  deposited  on  the  banks  of  the  rivers,  where  it  is  found 
in  lumps.  It  smells  of  pitch  mixed  with  asphalt." 


I  REFERENCES  BY  GREEK  AND  ROMAN  WRITERS  37 

In  reference  to  Indian  asphalt,  presumably  referring  to  the  de- 
posit at  the  Basti  river,  near  Isakhel,  India,  in  the  upper  Indus  Val- 
ley, he  comments  (I,  83)  : 

"Bitumen  obtained  in  India  is  prized  most  highly,  but  they  do 
not  disclose  the  locality  where  it  is  found.  It  is  so  desirable  because 
of  its  purple  hue,  its  heavy  weight  and  characteristic  strong  odor. 
The  dark  and  impure  varieties  of  asphalt  are  full  of  faults,  since 
they  have  been  mixed  with  pitch,  and  they  come  from  Phoenicia, 
Babylon,  Zacynthos  and  Sidon." 

He  states  that  asphalt  may  be  refined: 

"By  boiling  off  the  fluid  constituents,  which  make  the  material 
so  inflammable." 

Dioscorides  also  informs  us  that: 

"The  name  mumia  is  given  to  the  drug  called  'Bitumen  of 
Judea,'  and  to  the  mumia  of  the  tombs,  found  in  great  numbers  in 
Egypt,  and  which  is  nothing  more  than  a  mixture  which  the  Byzan- 
tine Greeks  useci  formerly  for  embalming  their  dead,  in  order  that 
the  bodies  might  remain  in  the  state  in  which  they  were  buried,  and 
experience  neither  decay  nor  change.  Bitumen  of  Judea  is  the  sub- 
stance which  is  obtained  from  the  Asphaltites  Lake." 

He  mentions  (V,  181)  that  "ampelitis"  comes  from  Selenica, 
and  "gagates"  from  Lycia  (V,  146)  ;  also  that  (I,  85)  : 

"Asphalt  is  recommended  as  a  panacea  against  skin  afflictions." 

Dion  Cassius  (155  to  230  A.D.}.  This  Roman  historian 
states : 70 

"There  is  Babylon,  Trajan  saw  the  asphalt  with  which  the  walls 
of  Babylon  had  been  built.  Together  with  bricks  or  stones,  it  pro- 
duces such  strength  that  the  walls  made  of  it  are  stronger  than  rock 
and  any  kind  of  iron." 

Philostratus  ( The  Elder]  —  (about  200  A.D.).  This  Athenian 
writer71  refers  (I,  23)  to  asphalt  deposits  near  Ardericca  (near 
the  present  town  of  Kirab)  in  Cissia  (Iran).  He  states  that  in 
the  land  of  Cissia: 

"The  soil  is  drenched  with  pitch  and  is  bitter  to  plant  in.  .  .  ." 

and  warns : 

"Against  drinking  water  which  has  been  in  contact  with  bitumen, 
since  this  will  cause  the  intestines  to  close  up,  owing  to  the  water 
taking  up  traces  of  bitumen." 

although  he  goes  on  to  say  ("Tetrabiblos,"  I,  2  and  49) : 


38  HISTORICAL  REVIEW  I 

"That  the  drinking  of  bituminous  water  is  the  best  remedy  for 
dropsy." 

He  also  describes  : 

"An  oil  which  once  set  afire,  cannot  be  extinguished,  and  which 
Indian  kings  use  to  burn  down  walls  and  capture  cities." 

Geoponica  (200  to  300  A.D.}.  The  "Geoponica"  72  consisted 
of  a  collection  of  writings  on  husbandry  and  agriculture  by  various 
Greek  and  Roman  writers  of  the  third  and  fourth  centuries,  includ- 
ing Gargilius  Martialis  of  Mauretania  and  Palladius  of  Rome.  In 
this  treatise  we  are  informed  that  a  mixture  of  bitumen  and  oil 
served  to  alleviate  wounds  in  trees  (XIII,  10  and  7) ;  that  rings  of 
bituminous  mastic  were  made  around  tree  trunks  for  protection 
against  ants;  that  bitumen  mixed  with  sulfur  was  burned  under  trees 
and  bushes  to  kill  caterpillars  and  other  harmful  insects,  also  for 
disinfecting  the  cages  of  birds  (XIV,  u,  4) ;  that  fowls  would  lay 
bigger  eggs  if  rubbed  with  a  mixture  of  bitumen,  resin  and  sulfur 
(XIV,  n);  that  a  mixture  of  bitumen  and  various  spices  served 
for  the  treatment  of  cattle  plague  (XVII,  16)  ;  and  lastly,  that  bi- 
tumen relieved  sufferers  of  diarrhoea  (XVII,  16,  i). 

Afrlcanus  (about  300  A.D.}.  This  Greek  writer,  in  his  treatise 
"Kestoi"  73  on  agriculture,  natural  history,  military  science,  etc.,  de- 
scribes a  mixture  consisting  of: 

"Sulfur,  natural  resin  (i.e.  asphalt),  salt  and  quicklime,  which 
by  careful  mixing,  the  addition  of  the  lime  last,  and  enclosing  the 
whole  in  a  bronze  vessel  to  exclude  humidity,  air  and  light,  will 
ignite  spontaneously  by  the  simple  addition  of  water  or  dew." 

Ammianus  Marcellmus  (330  to  395  A.D.}.  This  Roman  his- 
torian states,74  probably  in  reference  to  the  region  of  Quara  and 
Quala  Shergat  in  Iraq : 

"In  Assyria  there  is  asphalt  in  the  lake  called  Sosingite,  in  the 
bed  of  which  the  Tigris  is  absorbed,  which  flows  on  underground  to 
rise  to  the  surface  again  at  a  great  distance  away.  Naphtha  also 
occurs  here;  this  greatly  resembles  asphalt  and  is  very  viscous  and 
sticky.  Even  if  a  very  small  bird  alights  on  it,  it  is  drawn  down,  it 
can  no  longer  fly  and  it  disappears  into  the  depths.  ^  Once  this  kind 
of  substance  begins  to  burn,  human  intelligence  will  find  no  other 


I  ABOUT  1248  A.D.    PIERRE  DE  JOINVILLE  39 

means  of  quenching  it  than  by  earth.  A  big  cleft  will  be  seen  in 
these  districts  from  which  mortally  fatal  fumes  rise  up,  the  heavy 
odor  of  which  will  kill  any  living  creature  coming  within  its  reach." 

Theophanes  (758  to  817  A.D.}.  The  Greek  writer  Theopha- 
nes,  in  his  treatise  "Chronicles,"  states: 

"The  principle  of  spontaneous  ignition  by  contact  with  water 
was  brought  to  its  highest  practical  application  by  the  Greek  archi- 
tect Kallinikos  residing  in  Byzantium  about  650  A.D.,  as  a  fugitive 
from  the  Arabs  of  the  Syrian  town  of  Heliopolis,  and  who  was  the 
real  inventor  of  'Greek  Fire'."  75 

This  seems  strange,  in  view  of  the  earlier  disclosures  by  Thu- 
cydides(47i~40i  B.C.),  Hannibal  (247-183  B.C.),  Pliny  the  Elder 
(23-79  A.D.),  Philostratus  (about  200  A.D.),  and  others. 

About  950  A.D.  Abu-L-Hasan  Masudi.  The  Persian  writer 
Masudi,  in  his  "Annals"  76  refers  to  "oleum  de  gagantis,"  which  is 
an  oily  product  derived  from  natural  asphalt  by  a  process  termed 
"distillatio  per  decensorium"  which  was  carried  out  in  two  superim- 
posed jars  separated  by  a  screen  or  sieve.  The  upper  jar,  filled  with 
the  material  under  treatment,  was  heated  by  a  fire  and  the  oily  dis- 
tillate allowed  to  drip  through  the  screen  into  the  bottom  jar  im- 
bedded in  damp  soil.  Medieval  writers  frequently  refer  to  rock 
asphalts  and  asphaltites  under  the  name  "gagates,"  which  was  de- 
rived from  the  river  Gagas  or  Gages  in  Lycia,  Asia  Minor,  at  the 
mouth  of  which  there  was  stated  to  be  a  deposit  of  hard  asphalt. 
Gagates  were  used  as  a  means  of  exorcising  evil  spirits,  in  which 
connection  Bishop  Marbode  of  Rennes  (1067-1123  A.D.)  states  in 
his  treatise  "Dactyliothecae" : 

"As  an  amulet  it  benefits  dropsy,  diluted  with  water  it  prevents 
loose  teeth  from  falling  out,  whilst  fumigation  with  gagates  is  good 
for  epileptics.  It  remedies  indigestion  and  constipation,  cures  magi- 
cal illusions  and  evil  incantations,  and  is  often  used  in  love  potions." 

About  985  A.D.    Abd  Al  Mukaddasi.    This  writer  refers  7r  to: 

"Nafta  and  earth-pitch  from  Transoxania,  Ferghana," 
which  corresponds  to  the  present  Baku  region. 

About  1248  A.D.  Pierre  de  Joinville.  De  Joinville,  who  ac- 
companied King  Louix  IX  on  his  Sixth  Crusade  to  Damiette,  re- 
fers 78  to  the  use  of  Greek  Fire,  stating  that: 


40  HISTORICAL  REVIEW  I 

"Every  man  touched  by  it  believed  himself  lost,  every  ship  at- 
tacked was  devoured  by  flames." 

About  1300  A.D.  Marco  Polo.  This  Venetian  traveler  de- 
scribed 70  seepages  of  liquid  asphalt  at  Baku  on  the  Caspian  Sea. 
He  also  mentioned  the  existence  of  an  ancient  fire-temple  erected 
about  the  flaming  streams  of  gas  and  oil,  which  we  are  informed 
constituted  a  place  of  Hindoo  pilgrimage. 

About  1350  A.D.  Sir  John  Mandeville.  This  British  writer 
states  (Chap.  XXX):80 

"And  two  myle  from  Jericho  is  flom  Jordan  and  you  shall  wcte 
the  Dead  Sea  is  right  bitter,  and  this  water  casteth  out  a  thing 
called  asphatum,  as  great  pieces  as  a  horse." 

1494-1555.  Georg  Agricola.  This  well  known  German  metal- 
lurgist states : 81 

"Bitumen  is  produced  from  mineral  waters  containing  oil,  also 
from  liquid  bitumen,  and  from  rocks  containing  bitumen.  .  .  . 
Liquid  bitumen  sometimes  floats  in  large  quantities  on  the  surface  of 
wells,  brooks  and  rivers,  and  is  collected  with  buckets  or  other  pots. 
Small  quantities  are  collected  by  means  of  feathers,  linen  towels 
and  the  like.  The  bitumen  easily  adheres  to  these  objects,  and  is 
collected  in  big  copper  or  iron  vessels  and  the  lighter  fractions  evap- 
orated by  heating.  The  residual  oil  is  used  for  different  purposes 
and  some  people  mix  it  with  pitch,  others  with  used  axle  oil  to  make 
it  thinner.  The  bitumen  does  not  harden,  even  during  the  time  of 
its  heating  in  the  vessels.  Rocks  which  contain  bitumen  are  treated 
in  the  same  way  as  those  which  contain  sulfur,  by  heating  them  in 
vessels  with  a  sieve  bottom.  This,  however,  is  not  the  common 
practice,  because  the  bitumen  prepared  in  this  way  is  not  very  valu- 
able." This  process  is  illustrated  in  Fig.  23. 

Agricola  also  refers  to  asphaltic  crude-oil  seepages  at  Wietze, 
near  Hannover,  Germany,  and  mentions  the  use  of  "heavy  petro- 
leum to  protect  woodwork  from  rain." 

1498.  Christopher  Columbus.  On  his  third  voyage  to  America 
on  July  31,  1498,  Columbus  discovered  the  island  of  Trinidad, 
where  it  has  been  stated: 82  "He  careened  his  galleons  and  caulked 
their  storm-racked  seams  with  this  natural  waterproofing  material," 
referring  to  asphalt  derived  from  Trinidad  Lake, 


I  1563.    CESAR  FREDERICKE  41 

About  1500.  Use  of  Asphalt  in  Peru.  It  has  been  established 
that  the  Incas  of  Peru  constructed  an  elaborate  system  of  highways, 
some  of  which  were  paved  with  a  composition  not  unlike  modern 
bituminous  macadam. 

1535.  Discovery  of  Asphalt  in  Cuba.  G.  F.  Oviedo  y  Valdes 
of  Spain  describes  83  a  spring  of  semi-liquid  asphalt  in  the  Province 
Puerto  Principe,  near  the  coast  of  Cuba,  which  was  used  for  paint- 
ing the  hulls  of  ships.  Another  occurrence  is  mentioned  on  the 


From  Agricola 
FIG.  23.— -Smelting  Bitumen  from  Bituminous  Rock. 

shore  of  Havana  harbor,  used  for  similar  purposes.  He  tells  us 
that  asphaltic  petroleum  was  used  to  protect  woodwork  and  ma- 
sonry in  Cuba  as  early  as  1550  A.D. 

1563.  Cesar  Fredericke.  This  writer  in  his  publication  "Voy- 
age to  the  East  Indies,"  states  : 

"These  barks  of  the  Tigris  have  no  pumps  in  them,  because  of 
the  great  abundance  of  pitch,  which  they  have  to  pitch  them  with  all. 
This  pitch  they  have  in  abundance  two  days'  journey  from  Babylon. 
Near  unto  the  river  Euphrates,  there  is  a  city  called  Heit  (Hit), 
near  unto  which  city  there  is  a  great  plaine  full  of  pitch,  very  mar- 


42  HISTORICAL  REVIEW  1 

vellous  to  beholde,  and  a  thing  almost  incredible  that  out  of  a  hole 
in  the  earth,  which  continually  throweth  out  pitch  into  the  aire  with 
continuall  smoake ;  this  pitch  is  thrown  with  such  a  force  that  being 
hot  it  falleth  like  as  it  were  sprinckled  over  all  the  plame  in  such 
abundance  that  the  plaine  is  always  full  of  pitch.  The  Mores  and 
the  Arabians  of  that  place  say  that  that  hole  is  the  mouth  of  hell, 
and  in  truth  it  is  a  thing  very  notable  to  be  marked.  And  by  this 
pitch  the  whole  of  the  people  have  their  benefit  to  pitch  their  barks. 

1595.  Sir  Walter  Raleigh.  Sir  Walter  Raleigh  84  gives  a  record 
of  his  voyage  of  exploration  to  the  east  coast  of  South  America  in 
1595,  wherein  he  describes  his  visit  to  the  Island  of  Trinidad,  and 
gives  an  account  of  the  so-called  "Pitch  Lake,"  of  which  he  wrote: 

"March  22,  1595 — At  this  point  called  Tierra  de  Brea  or  Piche, 
there  is  that  abundance  of  stone  pitch,  that  all  the  ships  of  the 
world  may  be  therewith  laden  from  thence,  and  wee  made  trial  of 
it  in  trimming  our  shippes  to  be  most  excellent  goode  and  melteth  not 
with  the  sunne  as  the  pitch  of  Norway,  and  therefore  for  shippes 
trading  the  south  parts  very  profitable." 

1599.  First  Classification  of  Bituminous  Substances.  Andreas 
Libavius  refers  to  the  uses  of  asphalt,  and  classified  it  with  mineral 
oil,  amber  and  pitch.  He  endeavored  to  trace  the  connection  be- 
tween asphalt  and  petroleum,  and  gives  a  record  of  the  earliest 
literature  on  asphalt  including  the  works  of  Pliny,  Dioscorides, 
ftippocrates  and  others.85 

1608.  William  Shakespeare.  In  his  play  "Pericles"  written  in 
1608,  by  Shakespeare  (1564-1616),  occurs  the  passage:  "We  have 
a  chest  beneath  the  hatches,  caulked  and  bitumened  ready." 

1656.  Early  Dictionary  Definition  of  "Bitumen."  In  one  of 
the  earliest  dictionaries  of  the  English  language,  "Thomas  Blount's 
Glossary,"  bitumen  is  defined  as: 

"A  kind  of  clay  or  slime  naturally  clammy,  like  pitch,  growing 
in  certain  countries  of  Asia." 

It  is  interesting  to  note  the  connection  between  this  interpreta- 
tion of  the  word,  and  the  reference  to  "slime"  and  "slimepit"  in 
"Genesis." 

1660.  John  Milton.  In  "Paradise  Lost,"  written  about  1660 
by  Milton  (1608-1674),  we  read:  "Blazing  cressets  fed  with 
naphtha  and  asphalts";  and  again:  "The  plain,  whereon  a  black 


I  1712-1730.  VAL  DE  TRACERS,  LIMMER,  SEYSSEL  DEPOSITS  43 

bituminous  gurge  boils  out  from  underground — the  mouth  of  hell." 
1661.  Commercial  Production  of  Wood  Tar.  The  earliest  ref- 
erence to  the  production  of  wood  tar  on  a  large  scale  by  the  dry 
distillation  of  wood,  occurs  in  Robert  Boyle's  "Chemistra  Scepticus," 
1 66 1.  This  industry  is  said  to  have  been  first  practiced  in  Norway 
and  Sweden. 

1672.  First  Accurate  Description  of  Persian  Asphalt  Deposits. 
Dr.  J.  Fryer  accurately  describes  the  occurrences  of  asphalt  in  the 
East  Indies  and  Persia,  in  his  book  uNine  Years'  Travels"  (1672— 
i68i).86      . 

1673.  Discovery  of  Elaterite.    The  first  description  of  elater- 
ite,  originally  found  at  Castleton  in  Derbyshire,  England,  under 
the  name  "Elastic  Bitumen,"  is  given  by  M.  Lister  in  the  Philo- 
sophical Magazine   and  Journal   of  Science  ^   London,    1673    (p. 
6179). 

1681.  Discovery  of  Coal  Tar  and  Coal-Tar  Pitch.  In  a  patent 
(No.  214)  taken  out  in  England  on  August  19,  1681,  by  Joachim 
Becher  and  Henry  Serle,  entitled  "A  new  way  of  makeing  pitch,  and 
tarre  out  of  pit  coale,  never  before  found  out  or  used  by  any  other," 
we  find  the  first  description  of  coal  tar  and  coal-tar  pitch,  as  well  as 
their  methods  of  production. 

1691.  Discovery  of  Illuminating  Gas  from  Coal.  Dr.  John 
Clayton,  dean  of  Kildare,  England,  experimented  with  the  inflam- 
mable gas  obtained  on  heating  coal  in  a  closed  retort.  He  filled 
bladders  with  this  gas  and  demonstrated  that  it  burnt  with  a  lumi- 
nous flame. 

1694.  Discovery  of  Shale  Tar  and  Shale-Tar  Pitch.  British 
Patent  No.  330,  of  1694  (Jan.  29),  entitled  4<Pitch,  tar  and  oyle, 
out  of  a  kind  of  stone  from  Shropshire,"  granted  Martin  Eele, 
Thomas  Hancock  and  William  Portlock,  contains  the  earliest  record 
of  the  manufacture  of  shale  tar  and  shale-tar  pitch. 

1712-1730.  Discovery  of  Val  de  Travers,  Limmer  and  Seyssel 
Asphalt  Deposits.  The  asphalt  deposit  at  the  Val  de  Travers  in 
the  Jura  Mountains,  Canton  of  Neuchatel,  Switzerland,  was  dis- 
covered by  the  Greek  Doctor  Eirinis  d'Eyrinys  in  1712,  and  de- 
scribed in  detail.87 

Some  give  Eyrinys  the  credit  of  having  likewise  discovered  the 
Limmer  asphalt  deposit  near  Hanover,  Germany,  in  1730,  but  this 


44  HISTORICAL  REVIEW  J 

has  not  been  definitely  established.  A  third  discovery  of  asphalt  by 
Eyrinys,  in  1735,  at  Seyssel  in  the  Rhone  Valley,  Department  of 
Ain,  France,  proved  to  be  one  of  the  most  important  deposits  in 
Europe.  This  has  been  worked  constantly  up  to  the  present  time, 
and  will  be  described  later. 

1772.  First  Use  of  Tar  for  Flat  Roofs.  Recent  researches 
ascribe  P.  J.  Marperger  of  Berngau,  near  Neumarkt  (in  the  vicin- 
ity of  Niirnberg,  Germany)  as  the  originator  of  tarred  roofs.  He 
described  the  following  method  of  covering  flat  roofs:  the  wooden 
boards  were  first  caulked  with  oakum,  then  sprinkled  alternately 
with  tar  and  a  mixture  of  fine  sand  with  iron  slag,  until  after  three 
or  four  such  treatments  a  fairly  thick  protective  covering  was  ob- 
tained.88 

1746.  Invention  of  the  Process  of  Refining  Coal  Tar.  On 
Dec.  2,  1746,  a  patent  (No.  619)  was  granted  in  England  to  Henry 
Haskins  disclosing:  "A  new  method  for  extracting  a  spirit  or  oil 
from  tar,  and  from  the  same  process  obtaining  a  very  good  pitch;" 
consisting  of  our  present  process  of  fractional  distillation  in  a  closed 
retort  connected  with  a  worm  condenser. 

1752.  Samuel  Foote.  The  English  dramatist  Foote  (1720- 
1777)  writes  in  his  book  "Taste,"  published  in  1752,  of  the  "salu- 
tary application  of  the  asphaltum  pot"  for  preserving  the  beautify- 
ing qualities  of  the  complexion.  At  this  time  it  was  claimed  by 
authorities  to  be. "a  sure  cure  for  ringworm,  boils,  gout,  epilepsy, 
blindness,  toothache  and  colic." 

1777.  First  Exposition  of  Modern  Theory  of  the  Origin  of 
Asphalt.  In  his  "Elements  de  Mineralogie,"  published  in  1777 
LeSage  89  classified  bitumens  in  the  sequence :  "Naphtha,  petroleum, 
mineral  pitch,  maltha  and  asphalt,"  and  regarded  them  all  as  origi- 
nating from  petroleum  oil.  This  closely  conforms  to  the  modern 
views  regarding  the  classification  and  origin  of  bitumens. 

1788.  Discovery  of  Lignite  Tar.  Krimitz  in  1788  referred  to 
the  production  of  "a  tar-like  oil"  upon  destructively  distillating 
"earth  coal"  (lignite).  This  was  virtually  the  first  description  of 
the  manufacture  of  lignite  tar. 

1780-1790.  Discovery  of  "Composition"  or  "Prepared"  Roof- 
ing. Arvicl  Faxe  of  Sweden  9d  is  given  credit  for  having  produced 
the  first  composition  roofings  between  the  years  1780  and  1790  in 


I          1815.     COMMERCIAL  EXPLOITATION  OF  COAL-TAR  SOLVENTS        45 

the  following  crude  manner :  the  roof  boards  were  first  covered  with 
plain  paper,  impregnated  with  a  mixture  of  copper  and  iron  sul- 
fates,  which,  after  being  nailed  in  place,  was  coated  with  heated 
wood  tar  to  make  it 'waterproof,  and  then  surfaced  with  various 
colored  mineral  earths. 

A  newspaper  published  in  Leipsic  in  the  year  1791  credits 
Michael  Kag  of  Miihldorf,  Bavaria,  with  having  produced  an  im- 
proved form  of  prepared  roofing  by  saturating  raw  paper  with  var- 
nish, and  coating  the  surfaces  with  a  mineral  powder.  The  product 
was  also  recommended  as  a  substitute  for  leather  in  the  soles  of 
shoes. 

Similarly,  the  Magdeburg  Zeitung  on  Nov.  16,  1822,  contained 
a  notice  stating  that  paper  impregnated  with  tar  is  being  used  to 
displace  straw  and  wooden  shingles  for  roofing  purposes,  and  that 
the  former  may  be  made  fire-resistant  by  treating  the  tar  with 
unslaked  lime  and  surfacing  with  sand. 

The  manufacture  of  "tarred  board"  for  roofing  purposes,  as 
practiced  in  Germany  during  the  year  1828,  was  published  by  W.  A. 
Lampadius.01 

1792-1802.  Manufacture  of  Coal  Gas  and  Coal  Tar  on  a  Large 
Scale.  Wm.  Murdoch,  of  England,  was  the  first  to  manufacture 
coal  gas  and  coal  tar  on  a  large  scale. 

1797-1802.  Exploitation  of  Seyssel  Asphalt  in  France.  M. 
Secretan  obtained  a  concession  from  the  French  Government  to 
work  the  asphalt  deposits  at  Seyssel  on  the  Rhone,  France,  in  the 
fifth  year  of  the  French  Republic  (1797).  The  venture,  however, 
did  not  prove  a  success.  The  deposit  was  next  taken  over  by  Count 
de  Sassenay,  of  France,  in  1802,  and  actively  exploited.  A  labora- 
tory was  erected  to  investigate  the  uses  of  this  asphalt,  which  was 
marketed  in  France  under  the  name  "rock  asphalt  mastic,"  and  used 
for  surfacing  floors,  bridges  and  sidewalks,  also  to  a  limited  extent 
for  waterproofing.  The  earliest  experimental  use  was  in  the  vicinity 
of  Bordeaux  and  Lyons. 

1815.  Commercial  Exploitation  of  Coal-Tar  Solvents.  In 
1815,  F.  C.  Accum,  of  England,  obtained  "naphtha"  by  subjecting 
coal  tar  to  fractional  distillation  on  a  commercial  scale.  This  distil- 
late was  used  in  the  manufacture  of  India  rubber  goocfc,  for  burn- 
ing in  open  lamps  and  for  certain  kinds  of  varnish.  The  tar  which 


46  HISTORICAL  REVIEW  I 

remained  behind  had  no  particular  value  and  was  accordingly  con- 
sumed as  fuel. 

1820.  Manufacture  of  Asphalt-saturated  Packing  Papers  in 
Switzerland.  The  asphalt  deposits  previously  discovered  at  Neu- 
chatel,  Switzerland,  were  utilized  in  1820  for  impregnating  porous 
paper,  for  use  as  tarpaulins,  packing  paper,  imitation  oil-cloth,  etc., 
and  the  first  factory  was  established  in  Geneva.92 

1822.  Discovery  of  Scheererite  and  Hatchettite.  The  mineral 
wax  Scheererite  was  discovered  in  a  bed  of  lignite  (brown  coal)  at 
Uznach,  near  St.  Gall  in  Switzerland,  by  Captain  Scheerer,  in 
i823.93  In  the  same  year  the  mineral  wax  hatchettite  or  hatchetine 
was  discovered  on  the  borders  of  Loch  Fyne,  in  Argyllshire,  Scot- 
land, and  was  named  after  the  English  chemist,  C.  Hatchctt.94 

1830.  Discovery  of  Paraffin  Wax.  The  discovery  of  paraffin 
wax  is  credited  to  Carl  von  Reichcnbach,  of  Stuttgart,  Germany, 
who  was  the  first  to  describe  its  physical  and  chemical  properties.95 
He  derived  the  material  from  lignite  tar  and  christened  it  "paraffin" 
(parum  affinis),  because  of  its  unusual  resistance  to  chemicals. 

1832.  Coal  Tar  First  Used  for  Paving.      The  first  stretch  of 
tar-macadam  pavement  on  record  was  laid  in  Gloucestershire,  Eng- 
land, between  1832  and  1838.     In  this  same  connection,  an  inter- 
esting pioneer  patent  was  granted  to  Cassell  in  1834,  describing  the 
use  of  coal  tar  for  surfacing  roads,  grouting,  and  the  construction 
of  tar-concrete  paving  blocks.96 

1833.  Discovery  of  Ozokerite.    The  first  reference  to  the  min- 
eral ozokerite  was  by  E.  F.  Glocker  97  in  1833.     lie  discovered  it 
near  the  town  of  Slanik  in  Moldavia,  close  to  a  deposit  of  lignite 
at  the  foot  of  the  Carpathians.     It  was  named  from  the  Greek 
words  signifying  uto  smell"  and  "wax,"  in  allusion  to  its  odor. 

1835.  First  Asphalt  Mastic  Foot  Pavements  Laid  in  Paris. 
It  is  recorded  that  on  June  15,  1835,  the  first  mastic  pavement  was 
laid  at  Pont  Royal,  Paris,  composed  of  Scyssel  asphalt.98 

1836.  Asphalt  First  Used  in  London  for  Foot  Pavements. 
In   1836  we  first  hear  of  Seyssel  asphalt  being  introduced  from 
France  to  London  for  constructing  foot  paths.99 

1837.  Publication  of  First  Exhaustive  Treatise  on  the  Chem- 
istry of  Asphalt.    The  well-known  treatise  "Memoir  sur  la  compo- 
sition des  bitumes"  was  published  by  J.  B.  Boussingault  in  the  year 


I          1850.  DISCOVERY  OF  "ASPHALTIC  COAL"  IN  NEW  BRUNSWICK     47 

1837.  It  was  the  most  exhaustive  treatise  on  the  subject  which  had 
yet  appeared,  and  was  the  first  to  propose  the  use  of  the  terms 
"petrolene"  and  "asphaltene"  for  the  components  of  asphalt100 

1837.  Discovery  of  Bituminous  Matter  in  the  United  States. 
In  1837  appeared  the  first  report  of  an  asphalt  deposit  in  the  United 
States  in  which  semi-solid  and  solid  bitumens  were  reported  in  the 
Connecticut  valley  at  Farmington,  Hartford  (Rocky  Hill),  Berlin, 
Middletown  and  New  Britain,  Conn.101 

1838.  Discovery  of  Process  for  Preserving  Wood  with  Coal- 
tar  Creosote.    In  1838  Bethell  disclosed  the  use  of  coal-tar  oil  for 
impregnating  wood.102 

1838.  Asphalt  First  Used  in  the  United  States  for  Foot  Pave- 
ments. The  earliest  case  on  record  of  rock  asphalt  being  used  in 
the  United  States  for  sidewalks  is  in  the  portico  of  the  old  Mer- 
chants' Exchange  Building,  Philadelphia,  in  1838.  Seyssel  asphalt 
was  used  for  this  purpose. 

1841.  First  Use  of  Wood  Block  Pavement.  Wood  blocks  im- 
pregnated with  coal  tar  were  first  used  in  England.103 

1843.  Bituminous  Matters  Discovered  in  New  York  State. 
L.  C.  Beck,  in  1843,  wrote  a  paper  on  the  occurrence  of  bituminous 
matter  in  several  of  the  New  York  limestones  and  sandstones.104 

1844-1847.  First  Composition  Roofing  in  the  United  States. 
Rev.  Samuel  M.  Warren  reported  that  in  1844-1845  roofs  were 
first  laid  in  Newark,  N.  J.,  consisting  of  square  sheets  of  ship's 
sheathing  paper  treated  with  a  mixture  of  pine  tar  and  pine  pitch, 
and  surfaced  with  sand.  In  1847  coa^  tar  was  used  as  a  substitute 
for  the  pine  tar,  to  soften  the  pine  pitch,  and  employed  as  a  saturant 
for  the  paper.  Fine  gravel  was  next  used  to  substitute  the  sand. 
The  square  sheets  were  dipped  into  the  melted  mixture  by  hand, 
sheet  by  sheet,  and  then  the  excess  was  pressed  out  The  next  step 
consisted  in  running  the  paper  or  felt  in  rolls  through  continuously 
operating  saturators  designed  to  saturate  with  tar.  Finally,  in 
Buffalo,  N.  Y.,  coal  tar  was  distilled  down  to  a  roofing  pitch,  which 
was  used  to  replace  the  more  expensive  mixture  of  pine  pitch  and 
coal  tar.  The  foregoing  constituted  *  the  origin  of  the  "tar-and- 
gravel  roof,"  so  extensively  used  to-day.105 

1850.  Discovery  of  "Asphaltic  Coal"  in  New  Brunswick, 
Nova  Scotia.  C.  T.  Jackson  published  the  first  accounts  of  Nova 


48  HISTORICAL  REVIEW  I 

Scotia  "albertite"  in  the  years  1850-1851.  It  was  described  as 
"Albert  Coal."  106 

1852.  First  Modern  Asphaltic  Road.  The  first  asphaltic  road 
of  which  we  have  a  record  in  comparatively  modern  times,  was  con- 
structed in  1852  from  Paris  to  Perpignan,  France,  after  the  fashion 
of  modern  macadam  construction,  from  Val  de  Travers  rock- 
asphalt. 

1854.  First  Compressed  Asphalt  Roadway  Laid  in  Paris. 
In  1854  a  short  stretch  of  compressed  rock  asphalt  roadway  was 
laid  in  Paris  by  M.  Vaudrey.107  This,  we  are  told,  was  the  outcome 
of  observations  previously  made  by  a  Swiss  engineer,  M.  Merian, 
who  in  1849  noted  that  fragments  of  rock  asphalt  which  fell  from 
the  carts  transporting  the  material  from  the  mine  at  Val  de  Travers, 
to  the  nearby  village,  became  compressed  in  summer  under  the 
wheels  into  a  crude  pavement  of  asphalt.  M.  Leon  Malo  in  con- 
junction with  M.  Vaudrey  and  M.  Homberg  thereupon  con: 
structed  a  stretch  of  roadway  compacted  with  a  roller  in  the 
Rue  Bergere,  Paris,  which  was  maintained  in  good  condition  for 
sixty  years.108 

1858.  First  Modern  Asphalt  Pavement  Laid  in  Paris.  In 
1858  the  first  large  area  of  asphalt  roadway  was  constructed  on  the 
Palais  Royal  and  on  the  Rue  St.  Honore  in  Paris.  It  was  cortiposed 
of  a  foundation  of  concrete  6  in.  thick  surfaced  with  rock  asphalt 
mastic  obtained  from  the  Val  de  Travers  deposit,  compressed  to  a 
layer  about  2  in.  thick.  This  constituted  the  earliest  use  of  sheet 
asphalt  pavement  in  its  modern  form. 

1863.  Discovery  of  Grahamite  in  West  Virginia.  The  first 
account  of  the  West  Virginia  grahamite  deposit  is  given  by  J.  P. 
Lesley.100  The  material  was  described  as  a  "rock  asphalt,"  but  was 
later  named  "grahamite"  by  Henry  Wurtz,  in  honor  of  the  Messrs. 
Graham,  who  were  largely  interested  in  the  mine. 

1869.  The  First  Compressed  Asphalt  Pavement  in  London. 
The  first  stretch  of  asphalt  roadway  in  London  was  laid  at  Thread- 
needle  Street  near  Finch  Lane  in  May,  1869.  It  was  composed  of 
Val  de  Travers  rock  asphalt.1*0 

1870-1873.  First  Asphalt  Roadways  in  the  United  States. 
Some  give  the  Belgian  chemist,  E.  J.  De  Smedt,  credit  for  having 
the  first  rock  asphalt  roadway  in  tu~  TT~:ted  Statesr  contending 


I  1885.    DISCOVERY  OF  UINTMITE   (GILSONITE)   IN  UTAH  49 

that  in  1870  a  small  experimental  strip  was  laid  with  continental 
asphalt  opposite  the  City  Hall  in  Newark,  N.  J.  In  1871  pavements 
were  laid  in  Washington,  D.  C,  in  accordance  with  a  patent  granted 
to  N.  B.  Abbott,111  composed  of  a  mixture  of  crushed  rock  and  sand 
with  coal-tar  pitch  and  creosote  oil,  after  a  favorable  report  had 
been  rendered  by  a  special  commission  appointed  by  Congress. 
These  pavements  gave  good  service  for  over  15  years.  Also  in 
1871,  a  small  stretch  of  pavement  was  laid  in  Battery  Park,  New 
York  City,  and  according  to  T.  H.  Boorman,112  in  1872  a  larger 
stretch  was  laid  at  Union  Square,  composed  of  Val  de  Travers  rock 
asphalt.  It  is  also  reported  that  in  1873  a  similar  pavement  was 
laid  in  front  of  the  Worth  Monument,  which  remained  in  use  until 
i886.113 

1876.  First  Trinidad  Asphalt  Pavement  Laid  in  the  United 
States.  According  to  Clifford  Richardson  114  the  first  sheet  asphalt 
pavement  of  Trinidad  asphalt  to  be  laid  in  the  United  States  was  on 
Pennsylvania  Avenue,  Washington,  D.  C.  This  was  authorized  by 
an  act  of  Congress  passed  in  1876,  Val  de  Travers  rock  asphalt 
being  used  from  the  Capitol  to  Sixth  Street,  and  Trinidad  asphalt 
for  the  remainder.  The  rock  asphalt  wras  subsequently  pronounced 
to  be  too  slippery  and  the  Trinidad  asphalt  pavement  a  success. 

1880.  Use  of  Asphalt  "Chewing-gum"  in  Mexico.     B.  de 
Sahagun  115  informs  us  that  the  inhabitants  of  the  coastal  districts  of 
Mexico,  the  Totonacs,  collected  asphalt  ("tzacutli")  in  the  Panuco 
river  region  and  sold  it  to  the  Aztecs  of  the  interior,  who  in  turn 
compounded  it  with  gum  chicle  ("txixtli")  and  used  the  mixture  as 
chewing-gum  ( "chapopotli" ) . 

1881.  Use  of  Chemicals  for  Oxidizing  Coal  Tars  and  Petro- 
leum Asphalts.     The  first  complete  disclosure  of  the  process  for 
"oxidizing"  bituminous  materials  was  by  E.  J.  De  Smedt.116    This 
process  consisted  in  evaporating  coal  tar  or  asphalt  in  contact  with 
substances  capable  of  inducing  oxidation   (such  as  potassium  per- 
manganate), "to  give  them  greater  tenacity  and  render  them,  or  the 
pavement,  or  other  compositions  in  which  they  enter,  less  brittle  and 
less  liable  to  be  affected  by  air  or  water." 

1885.  Discovery  of  Uintaite  (Gilsonite)  in  Utah.  Gilsonite, 
first  known  as  "uintaite,"  was  discovered  in  the  Uinta  Valley  near 
Fort  Duchesne,  Utah,  in  1885.  It  was  first  described  by  W.  P. 


50  HISTORICAL  REVIEW  I 

Blake 11T  and  was  later  called  "gilsonite,"  after  S.  H.  Gilson,  of 
Salt  Lake  City. 

1889.  Discovery  of  Wurtzilite  in  Utah.  W.  P.  Blake  subse- 
quently discovered  a  deposit  of  wurtzilite  not  far  from  the  source  of 
gilsonite  in  the  Uinta  Valley,  Wasatch  County,  Utah,  between  Salt 
Lake  and  the  valley  of*the  Green  river.118  It  was  named  after  Dr. 
Henry  Wurtz  of  New  York. 

1891.  Exploitation  of  the  Bermudez  Asphalt  Deposit,  Vene- 
zuela.   According  to  Hippolyt  Kohler  and  Edmund  Graefe,119  the 
Bermudez  asphalt  deposit  in  Venezuela  was  first  developed  in  the 
year  1891  by  the  New  York-Bermudez  Company,  and  subsequently 
taken  over  by  the  Barber  Asphalt  Paving  Co.    A  search  of  the  lit- 
erature fails  to  reveal  when  this  deposit  was  first  discovered. 

1892.  Use  of  Bermudez  Asphalt  on  a  Large  Scale.    Bermudez 
asphalt  was  first  used  extensively  in  Detroit,  Mich.,  in  1892,  and 
the  year  following  in  Washington,  D.  C    With  this  start,  it  rapidly 
gained  in  popularity,  and  is  to-day  largely  used  as  a  road  binder,  as 
well  as  for  sheet-asphalt  pavements. 

1894.  Use  of  Air  for  Oxidizing  Petroleum  Asphalt.  A  further 
development  of  the  De  Smedt  process  for  oxidizing  petroleum  as- 
phalt was  brought  about  by  F.  X.  Byerley,  of  Cleveland,  O.,  who 
blew  air  through  asphaltic  oils  maintained  at  a  temperature  of 
600°  F.120  The  resulting  product,  marketed  under  the  name  of 
"byerlite,"  attained  great  popularity. 


CHAPTER  II 

TERMINOLOGY  AND  CLASSIFICATION  OF  BITUMINOUS 

SUBSTANCES 

One  of  the  most  baffling  problems  with  which  we  have  had  to 
deal  in  recent  years  is  fixing  the  definitions  of  the  various  bituminous 
substances,  and  the  products  in  which  they  are  used  in  the  arts.1 

The  words  "bitumen,"  "asphalt/'  "resin,"  "tar,"  "pitch," 
"wax,"  have  been  in  use  for  many  centuries,  most  of  them  long 
before  the  advent  of  the  English  language.  At  first,  very  little  was 
known  regarding  the  properties  of  these  substances,  and,  as  a  result, 
the  early  writers  used  these  terms  loosely,  and,  in  many  cases,  inter- 
changeably. It  is  probable  that  each  of  these  words  at  first  related 
to  the  aggregate  characteristics  of  some  typical  substance  closely 
associated  with  the  processes  of  daily  life.  As  nothing  of  the  chem- 
istry was  known  when  these  terms  originated,  they  were  at  first 
differentiated  solely  by  their  physical  characteristics. 

The  words  originally  had  but  a  limited  meaning,  but  as  new 
members  of  these  groups  of  substances  were  discovered,  the  terms 
were  extended  in  scope  until  the  various  expressions  completely  out- 
grew their  original  bounds.  This  resulted  in  a  certain  amount  of 
overlapping  and  ambiguity. 

As  the  chemistry  of  these  substance  gradually  became  known, 
this  means  was  likewise  adopted  to  differentiate  between  them,  but 
we  are  still  compelled  to  rely  principally  upon  the  physical  charac- 
teristics in  arriving  at  a  rational  basis  of  terminology,  as  their  chem- 
istry has  been  unravelled  to  but  a  limited  extent. 

In  defining  a  substance,  we  must  rely  on  one  or  more  of  the  fol- 
lowing criteria : 

Origin,  Solubility, 

Physical  Properties,  Chemical  Composition. 

The  last  three  can  be  more  or  less  readily  ascertained  from  an 
examination  of  the  substance  itself.  The  origin,  however,  is  not 

51 


52  TERMINOLOGY  AND  CLASSIFICATION  II 

always  apparent,  but  in  certain  cases  may  be  deduced  by  inference. 
To  base  a  definition  solely  upon  a  statement  of  the  origin  of  a  sub- 
stance would  necessitate  some  prior  knowledge  concerning  its  source 
or  mode  of  production.  As  such  knowledge  is  not  always  available, 
a  definition  of  this  kind  would  be  very  limited  in  its  scope.  Unfor- 
tunately, this  plan  has  often  been  followed  by  many  of  the  leading 
technical  societies  in  this  country  and  abroad,  in  fixing  the  defini- 
tions of  bituminous  substances. 

A  far  better  method  consists  in  basing  the  definition  upon  the 
inherent  characteristics  of  the  substance  itself,  so  as  to  permit  of  its 
identification  without  necessarily  having  prior  knowledge  concerning 
its  origin. 

The  four  cardinal  features  forming  this  latter  basis  of  nomencla- 
ture may  be  further  elaborated  as  shown  in  Table  I. 

In  Table  II  the  principal  types  of  bituminous  substances  are 
classified  according  to  the  features  enumerated  in  Table  I. 

The  definitions  which  follow  are  based  upon  this  classification. 
Although  reference  is  made  to  the  origin  of  the  substance,  neverthe- 
less, this  is  but  incidental,  and  with  the  exception  of  the  generic 
terms,  the  definitions  would  be  explicit  even  though  this  feature  were 
omitted. 

Bituminous.  Substances.*  A  class  of  native  and  pyrogenoust 
substances  containing  bitumens  or  pyrobitumens,  or  resembling 
them  in  their  physical  properties. 

SCOPE.  This  definition  includes  bitumens,  pyrobitumens,  py- 
rogenous  distillates  and  tars,  pyrogenous  waxes  and  pyrogenous  resi- 
dues (pitches  and  pyrogenous  asphalts). 

Liquid  Bituminous  Materials.  Those  having  a  penetration  at 
25°  C.  (77°  F.),  under  a  load  of  50  g.  applied  for  one  second, 
of  more  than  350  (Test  gb). 

Semi-Solid  Bituminous  Materials.    Those  having  a  penetration 

*  The  scope  of  the  word  "bituminous*'  is  based  on  the  commonly  accepted  interpreta- 
tion of  the  suffix  "ous,"  signifying:  (i)  to  contain;  (2)  to  resemble,  to  partake  of  the 
nature,  to  have  the  qualities  (e.g.,  silicious:  containing  silica  or  resembling  silica; 
resinous:  containing  or  resembling  resin;  oleaginous:  containing  or  resembling  oil;  cal- 
careous:, containing  or  resembling  lime).  Similarly,  the  word  "bituminous"  is  construed 
to  include  substances,  either  containing  more  or  less  bitumen  (or  pyrobitumen),  or  else 
resembling  them  in  their  appearance  or  qualities. 

fThe  expression  "pyrogenous"  implies  that  the  substance  was  produced  by  means  of 
heat  or  fire. 


II 


BITUMINOUS  SUBSTANCES 


Origin 


Solubility 

Chemical 
Compo- 
sition 


Native 


Pyrogenous 


TABLE  I 

r  Mineral 
I  Vegetable 
I  Animal 


Factional  distillation 
Destructive  distillation 
Heating  in  a  closed  vessel 
Blowing  with  air. 


Color  in  Mass     H 

r  Light  (white,  yellow  or  brown) 
Dark  (black) 

Consistency 
or  Hardness 

Liquid 
Viscous 
Semi-solid 
Solid 

Fracture             j 

Conchoid  al 
Hackly 

Physical 

Properties 

Lustre                 j 

:Waxy 
Resinous 
Dull 

Feel 


Odor 


Volatility 


Fusibility 


f  Adherent 
<  Non-adherent 
I  Unctuous  (waxy) 

I  Oily  (petroleum-like) 
I  Tarry 

f  Volatile 

(  Non-volatile 

f  Fusible 

]  Difficultly  fusible 

I  Infusible  (melts  only  with  decomposition) 


Non-mineral  constituents  soluble  in  carbon  disulfide 

Hydrocarbons  (compounds  containing  carbon  and  hydrogen) 
Oxygenated  bodies  (compounds  containing  carbon,  hydrogen,  and 

oxygen) 

Crystallizable  paraffins  (crystallize  at  low  temperatures) 
Mineral  matter  (inorganic  substances). 


at  25°  C.  (77°  F.)>  under  a  load  of  100  g.  applied  for  five  seconds, 
of  more  than  10,  and  a  penetration  at  25°  C.  (77°  F,)  ,  under  a  load 
of  50  g.  applied  for  one  second,  of  not  more  than  350  (Test  9^). 

Solid  Bituminous  Materials.  Those  having  a  penetration  at 
25°  C.  (77°  F.),  under  a  load  of  100  g.  applied  for  five  seconds,  of 
not  more  than  10  (Test 


54 


TERMINOLOGY  AND  CLASSIFICATION 


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II  BITUMEN  55 

IT 

Bitumen,*  A  generic  term  applied  to  native  substances  of  vari- 
able color,  hardness  and  volatility;  composed  principally  of  hydro- 
carbons, substantially  free  from  oxygenated  bodies ;  sometimes  asso- 
ciated with  mineral  matter,  the  non-mineral  constituents  being  fusible 
and  largely  soluble  in  carbon  disulfide,  yielding  water-insoluble  sul- 
fonation  products. 

SCOPE.  This  definition  includes  petroleums,  native  asphalts, 
native  mineral  waxes  and  asphaltites  (gilsonite,  glance  pitch  and 
grahamite). 

Pyrobitumen.t  A  generic  term,  applied  to  native  substances  of 
dark  color;  comparatively  hard  and  non-volatile;  composed  of  hy- 
drocarbons, which  may  or  may  not  contain  oxygenated  bodies; 
sometimes  associated  with  mineral  matter,  the  non-mineral  constitu- 
ents being  fusible  and  relatively  insoluble  in  carbon  disulfide. 

SCOPE.  This  definition  includes  the  asphaltic  pyrobitumens 
(elaterite,  wurtzilite,  albertite  and  impsonite)  also  the  non-asphaltit 
pyrobitumens  (peat,  lignite,  bituminous  coal  and  anthracite  coal) 
and  their  respective  shales. 

Petroleum.  A  species  of  bitumen,  of  variable  color,  liquid  con- 
sistency, having  a  characteristic  odor;  comparatively  volatile;  com- 
posed principally  of  hydrocarbons,  substantially  free  from  oxy- 
genated bodies;  soluble  in  carbon  disulfide,  yielding  water-insoluble 
stilfonation  products. 

SCOPE.  This  definition  includes  non-asphaltic,  semi-asphaltic 
and  asphaltic  petroleums. 

Mineral  Wax.  A  term  applied  to  a  species  of  bitumen,  also  to 
certain  pyrogenous  substances;  of  variable  color,  viscous  to  solid 
consistency;  having  a  characteristic  lustre  and  unctuous  feel;  com- 
paratively non-volatile;  composed  principally  of  saturated  hydro- 
carbons, substantially  free  from  oxygenated  bodies ;  containing  con- 
siderable crystallizable  paraffins;  sometimes  associated  with  mineral 

*  The  interpretation  of  the  term  "bitumen"  as  employed  in  this  treatise  is  entirely  dis- 
sociated from  the  idea  of  solubility  (in  certain  solvents  for  hydrocarbons),  and  has  no 
connection  whatsoever  with  the  inappropriate  expression  "total  bitumen,"  used  in  many 
contemporary  text-books  to  designate  the  amount  soluble  in  carbon  disulfide,  and  which 
unfortunately  is  largely  responsible  for  the  existing  confusion  in  terminology. 

fThe  expression  "pyrobitumen"  implies  that  the  substance  when  subjected  to  heat  or 
fire  will  generate,  or  become  transformed  into  bodies  resembling  bitumens  (in  their  solu- 
bility and  physical  properties). 


56  TERMINOLOGY  AND  CLASSIFICATION  II 

f 

matter,  the  non-mineral  constituents  being  easily  fusible  and  soluble 
in  carbon  disulfide,  yielding  water-insoluble  sulfonation  products. 

SCOPE.  This  definition  is  applied  to  crude  and  refined  native 
mineral  waxes,  also  to  pyrogenous  waxes.  Crude  native  mineral 
waxes  include  ozokerite.  Refined  native  mineral  waxes  include 
ceresine  (refined  ozokerite)  and  montan  wax  (extracted  from  lig- 
nite or  pyropissite  by  means  of  solvents).  Pyrogenous  waxes  in- 
clude the  solid  paraffins  separated  from  non-asphaltic  and  semi- 
asphaltic  petroleums,  peat  tar,  lignite  tar  and  shale  tar. 

Asphalt.  A  term  applied  to  a  species  of  bitumen,  also  to  certain 
pyrogenous  substances  of  dark  color,  variable  hardness,  compara- 
tively non-volatile;  composed  principally  of  hydrocarbons,  substan- 
tially free  from  oxygenated  bodies;  containing  relatively  little  to 
no  crystallizable  paraffins;  sometimes  associated  with  mineral  mat- 
ter, the  non-mineral  constituents  being  fusible,  and  largely  soluble 
in  carbon  disulfide,  yielding  water-insoluble  sulfonation  products. 

SCOPE.  This  definition  is  applied  to  native  asphalts  and  pyrog- 
enous asphalts.  Native  asphalts  include  asphalts  occurring  natur- 
ally in  a  pure  or  fairly  pure  state,  also  asphalts  associated  naturally 
with  a  substantial  proportion  of  mineral  matter.*  The  associated 
mineral  matter  may  be  sand,  sandstone,  limestone,  clay,  shale,  etc. 
Pyrogenous  asphalts  include  residues  obtained  from  the  distillation, 
blowing,  etc.,  of  petroleums  (e.g.,  residual  oil,t  blown  asphalts,t 
residua!  asphalts,!  sludge  asphalt,  1 1  etc.),  also  from  the  pyrogenous 
treatment  of  wurtzilite  (e.g.,  wurtzilite  asphalt  1T). 

In  Europe,  the  term  "asphalte"  is  applied  to  unconsolidated 
limestone  impregnated  with  asphalt,  which  softens  and  crumbles 
when  subjected  to  a  moderate  heat  (e.g.,  125°  to  1 60°  F.),  whereas 
the  term  "bituminous  rock"  is  used  to  designate  consolidated  lime- 
stone rock  impregnated  with  asphalt,  which  resists  high  tempera- 
tures (e.g.,  1000°  F.  and  over)  without  crumbling. 

Asphaltite.  A  species  of  bitumen,  including  dark-colored,  com- 
paratively hard  and  non-volatile  solids;  composed  principally  of 

*  Often  termed  "rock  asphalts." 

f  Produced  by  the  dry  distillation  of  non-asphaltic  petroleum,  the  dry  or  steam  dis- 
tillation of  semi-asphaltic  petroleum  and  the  steam  distillation  of  asphaltic  petroleum. 

t  Produced  by  blowing  air  through  heated  residual  oils. 

§  Produced  by  the  steam  distillation  of  semi-asphaltic  and  asphaltic  petroleums. 

||  Produced  from  the  acid  sludge  obtained  in  the  purification  of  petroleum  distillates 
with  sulfuric  acid. 

fl  Produced  by  depolymerizing  wurtzilite  in  closed  retorts. 


II  TAR  67 

hydrocarbons,  substantially  free  from  oxygenated  bodies  and  crys- 
tallizable  paraffins;  sometimes  associated  with  mineral  matter,  the 
non-mineral  constituents  being  difficultly  fusible,  and  largely  soluble 
in  carbon  disulfide,  yielding  water-insoluble  sulfonation  products. 

SCOPE.  This  definition  includes  gilsonite,  glance  pitch,  and 
grahamite. 

Asphaltic  Pyrobitumen.  A  species  of  pyrobitumen,  including 
dark-colored,  comparatively  hard  and  non- volatile  solids ;  composed 
of  hydrocarbons,  substantially  free  from  oxygenated  bodies ;  some- 
times associated  with  mineral  matter,  the  non-mineral  constituents 
being  infusible  and  largely  insoluble  in  carbon  disulfide. 

SCOPE.  This  definition  includes  elaterite,  wurtzilite,  albertite, 
impsonite  and  the  asphaltic  pyrobituminous  shales. 

Non-asphaltic  Pyrobitumen.  A  species  of  pyrobitumen,  inclucj- 
ing  dark-colored,  comparatively  hard  and  non-volatile  solids;  com- 
posed of  hydrocarbons,  containing  oxygenated  bodies ;  sometimes 
associated  with  mineral  matter,  the  non-mineral  constituents  being 
infusible,  and  largely  insoluble  in  carbon  disulfide. 

SCOPE.  This  definition  includes  peat,  lignite,  cannel  coal,  bitu- 
minous coal,  anthracite  coal,  and  the  non-asphaltic  pyrobituminous 
shales. 

Tar.  A  term  applied  to  pyrogenous  condensates  obtained  in  the 
destructive  distillation  of  organic  materials;  of  dark  color,  liquid 
consistency;  having  characteristic  odors;  comparatively  volatile  at 
high  temperatures;  composed  principally  of  hydrocarbons,  some- 
times associated  with  carbonaceous  matter,  the  non-carbonaceous 
constituents  being  largely  soluble  in  carbon  disulfide,  yielding  water- 
soluble  sulfonation  products. 

SCOPE.  This  definition  includes  the  volatile  oily  decomposition 
products  obtained  from  the  pyrogenous  treatment  of  petroleum 
(water-gas  tar  and  oil-gas  tar),  bones  (bone-tar),  wood  and  roots 
of  coniferae  (pine  tar),  hardwoods,  such  as  oak,  maple,  birch,  and 
beech  (hardwood  tar),  peat  (peat  tar),  lignite  (lignite  tar),  bitu- 
minous coal  (gas-wrorks  coal  tar,  coke-oven  coal  tar,  blast-furnace 
coal  tar,  producer-gas  coal  tar,  etc.),  and  pyrobituminous  shales 
(shale  tar). 


58  TERMINOLOGY  AND  CLASSIFICATION  II 

Pitch.  A  term  applied  to  pyrogenous  residues  obtained  in  the 
distillation  of  organic  materials;  of  dark  color,  viscous  to  solid  con- 
sistency; comparatively  non-volatile,  fusible;  composed  principally 
of  hydrocarbons;  sometimes  associated  with  carbonaceous  matter, 
the  non-carbonaceous  constituents  being  largely  soluble  in  carbon  di- 
sulfide,  yielding  water-soluble  sulfonation  products. 

SCOPE.  This  definition  includes  residues  obtained  from  the  dis- 
tillation of  tars  (oil-gas-tar  pitch,  water-gas-tar  pitch,  bone-tar 
pitch,  wood-tar  pitch,  peat-tar  pitch,  lignite-tar  pitch,  gas-works 
coal-tar  pitch,  coke-oven  coal-tar  pitch,  blast-furnace  coal-tar  pitch, 
producer-gas  coal-tar  pitch,  and  shale-tar  pitch) ;  also  from  the  dis- 
tillation of  fusible  organic  substances,  the  process  having  been  termi- 
nated before  the  formation  of  coke  (rosin  pitch  and  fatty-acid 
pitch) ;  also  anthracene  pitch,  naphthol  pitch,  cresol  pitch,  ozokerite 
pitch,  montan  pitch,  rubber  pitch,  gutta-percha  pitch,  etc.,  known  in 
Germany  as  "Immediate  Pitches,"  i.e.,  produced  directly  (immedi- 
ately) on  distillation,  without  the  initial  formation  of  tars,2 

In  Germany,  the  terms  "Chemopeche"  and  "Chemoasphalte" 
are  used  to  designate  pitches  and  asphalts,  respectively,  which  are 
produced  as  the  result  of  chemical  reactions,  including  the  fol- 
lowing : 8 

(a)  Precipitation  products,  resulting  from  the  precipitation  or 
selective  extraction  by  means  of  solvents. 

(b)  Oxygenated  products,  resulting  from  the  treatment  with 
air,  oxygen,  ozone,  etc.,  at  elevated  temperatures,  e.g.  blown  petro- 
leum asphalt,  blown  coal-tar  pitch,  etc. 

(c)  Hydrogenated  products,  resulting  from  treatment  with  hy- 
drogen in  the  presence  of  a  catalyst  at  elevated  temperatures,  and 
distillation  of  the  resultant  product. 

(d)  Reaction  with  mineral  acids  (i.e.,  sulfuric,  nitric,  phos- 
phoric, etc.)  and  evaporation  or  distillation  of  the  residue,  e.g. 
sludge  asphalt. 

(e)  Reaction  with  alkalies  and  subsequent  precipitation,  extrac- 
tion, or  distillation  of  the  resultant  product. 

(f)  Reaction  with  sulfur  or  sulfur  derivatives  at  elevated  tem- 
peratures, e.g.  sulfurized  asphalts  and  pitches. 

(g)  Reaction  with  halogens  (e.g.  chlorine,  iodine,  etc.). 
(h)   Reaction  with  phosphorus  and  its  derivatives. 

[i)  Reaction  with  metallic  salts;  either  solid  salts  at  elevated 
temperatures,  or  aqueous  solutions  of  metallic  salts  in  refining  op- 
erations, and  separation  of  the  resultant  polymerized  product 


II  BITUMINOUS  SUBSTANCES  59 

(j)  Reaction  with  sundry  chemicals  (e.g.  formaldehyde  and  its 
derivatives,  furfurol,  etc.). 

It  will  be  noted  that  the  terms  "asphalt"  and  "mineral  wax" 
are  each  applied  indiscriminately  to  native  and  pyrogenous  sub- 
stances. This  is  due  to  the  fact  that  at  the  present  time  it  is  prac- 
tically impossible  to  distinguish  between  certain  native  and  pyroge- 
nous asphalts  or  mineral  waxes,  either  by  physical  or  chemical  means. 
It  is  probable  that  some  method  may  be  discovered  for  accomplish- 
ing this,  in  which  event  it  would  be  of  decided  advantage  to  frame 
separate  definitions  to  distinguish  between  native  and  pyrogenous 
substances  respectively.  With  the  knowledge  available  at  present, 
however,  this  cannot  readily  be  accomplished.  We  must  be  content, 
therefore,  to  apply  the  terms  "asphalt"  and  "mineral  wax"  both  to 
native  substances  and  to  manufactured  (pyrogenous)  products. 

In  many  of  the  early  classifications,  natural  gas  and  marsh  gas 
were  included  within  the  scope  of  the  term  "bitumen."  As  this 
stretches  the  meaning  to  an  abnormal  extent,  the  author  deems  it 
inadvisable  to  include  natural  gases  in  the  definitions  and  classifica- 
tions given  in  this  treatise. 

The  terms  "maltha"  (derived  from  the  Greek  /*<IX0a),  "brea" 
and  "chapapote"  (of  Mexican  Spanish  origin),  "goudron  minerale" 
(French),  "Bergteer"  (German),  "kir"  (Russian),4  and  "mineral 
tar"  (English),  frequently  found  in  contemporary  classifications  to 
designate  the  softer  varieties  of  native  asphalt,  have  been  omitted 
for  the  sake  of  brevity. 

When  it  comes  to  classifying  bituminous  substances,  the  inter- 
pretation of  the  word  "bitumen"  represents  the  crux  of  the  entire 
matter.  An  analysis  of  the  views  concerning  the  scope  of  this  term, 
prevalent  in  America  and  abroad,  shows  that  they  may  be  grouped 
into  four  classes,  which  will  be  listed  in  the  order  of  their  breadth, 
commencing  with  the  one  having  the  narrowest  scope  : 

(a)  Bitumens — naturally  occurring  hydrocarbons. 

(b)  Bitumens — naturally  occurring  hydrocarbons,  likewise  resi- 

dues obtained  from  the  distillation  of  petroleum  (e.g., 
petroleum  asphalts). 

(c)  Bitumens — naturally  occurring  hydrocarbons,  likewise  resi- 

dues obtained  from  the  distillation  of  petroleum,  likewise 
artificial  hydrocarbon  substances  (e.g.,  tars  and  pitches). 


60  TERMINOLOGY  AND  CLASSIFICATION  II 

(d)  Bitumens — only  those  components  of  (c)  which  are  soluble 
in  carbon  disulfide. 

View  (a)  represents  the  layman's  interpretation  of  the  word,  as 
is  reflected  in  the  principal  dictionaries  of  both  abroad  and  America. 
It  is  obvious  from  these  definitions  that  the  word  ''bitumen''  has  for 
generations  been  confined  to  hydrocarbon  substances  which  occur 
in  nature,  and  distinctly  excludes  hydrocarbon  substances  produced 

artificially.  . 

View  (b)  is  supported  by  the  British  Engineering  Standards 
Association,  also  by  Dr.  Heinrich  Mallison  in  Germany.  This  in- 
volves a  slight  departure  from  View  (a),  including  as  it  does,  resi- 
dues obtained  from  the  distillation  of  petroleum. 

View  (c)  is  still  somewhat  broader  than  (b),  being  extended  to 
include  tars  and  pitches.  It  is  supported  abroad  by  David  Holde 
and  Wilhelm  Reiner  and  others.  , 

View  (d)  has  been  adopted  in  principle  by  the  American  Society 
for  Testing  Materials,5  and  the  American  Standards  Association. 

Now  the  question  arises  as  to  whether  there  is  any  need  or  justi- 
fication of  extending  the  dictionary  definitions  embodied  in  View 
(a).  In  other  words,  has  the  scientific  fraternity  the  right  to  change 
or  modify  what  has  been  the  common  heritage  of  the  people,  without 
some  particularly  good  reasons  ?  The  only  apparent  justification  for 
extending  the  scope  of  the  word  "bitumen"  as  reflected  in  Views  (b) 
and  (c)  is  to  include  certain  products  which  have  been  developed 
and  produced  since  the  word  was  originally  adopted — such  products 
as  petroleum  asphalts,  tars  and  pitches.  Parenthetically,  there 
seems  to  be  but  little  justification  to  extend  the  word  "bitumen" 
to  include  petroleum  asphalts  (as  outlined  in  View  &),  since  the 
prpcess  of  distillation  has  a  marked  effect  on  the  nature  of  the 
asphalt  originally  present  in  the  petroleum.  At  the  high  end-tem- 
peratures at  which  the  distillation  process  is  conducted  (600°  to 
800°  F.)  a  form  of  polymerization  takes  place,  whereby  asphalt-like 
substances  are  produced.  In  other  words,  the  percentage  of  asphalt 
in  the  petroleum  is  increased  under  these  conditions.  It  follows 
therefore,  that  the  petroleum  asphalts  produced  commercially,  differ 
in  their  physical  and  chemical  properties  from  the  asphalt  originally 
present  in  the  petroleum,  or  separated  in  nature  by  a  slow  natural 
process  of  evaporation. 

If  the  word  "bitumen"  is  broadened  in  accordance  with  View  (c) 


H  BITUMINOUS  SUBSTANCES  61 

it  will  become  synonymous  with  the  word  "bituminous  substance" 
so  that  both  expressions  will  have  an  identical  meaning. 

Singularly,  there  seems  to  be  but  very  little  difference  of  opinion 
at  the  present  time  with  respect  to  the  expression  * 'bituminous  sub- 
stance." In  this,  the  scientific  fraternity  seems  to  be  in  accord  with 
the  dictionary  definitions.  It  is  the  consensus  of  opinion  that  the 
expression  "bituminous  substance"  represents  a  form  of  substance 
which  contains  bitumens,  or  resembles  bitumens,  or  constitutes  the 
source  of  bitumens.  This  is  based  on  a  commonly  accepted  interpre- 
tation of  the  suffix  "ous,"  signifying: 

i — to  contain; 

2 — to  resemble,  to  partake  of  the  nature,  or  to  have  the  qual- 
ities of. 

This  raises  the  question  as  to  whether  or  not  language  as  it  exists 
at  present  does  not  furnish  us  with  sufficient  tools  to  answer  our 
needs.  Is  not  the  expression  "bituminous"  ("bituminous  sub- 
stance") of  sufficient  breadth  to  include  "bitumens"  (i.e.,  naturally 
occurring  hydrocarbons)  as  well  as  petroleum  asphalts,  tars  and 
pitches?  Is  it  not  true  that  petroleum  asphalts,  tars  and  pitches 
resemble  "bitumens"  or  partake  of  their  nature  in  respect  to  their 
physical  properties?  Then  why  broaden  the  scope  of  the  word  "bi- 
tumen" so  as  to  make  it  synonymous  with  the  expression  "bituminous 
substance"?  The  author  can  see  no  justification  or  necessity  for  so 
doing. 

Moreover,  View  (d)  is  so  technical,  that  it  is  questionable 
whether  the  laity  will  ever  accept  it.  Its  proponents  maintain  that 
the  only  way  to  determine  whether  or  not  a  substance  is  a  "bitumen" 
is  to  subject  it  to  chemical  analysis,  to  find  out  what  proportion  is 
soluble  in  carbon  disulfide.  According  to  this  view,  the  presence  of 
any  associated  mineral  constituents  or  hydrocarbons  insoluble  in 
carbon  disulfide  would  disqualify  the  original  substance  as  a  "bitu- 
men"— even  though  it  occurred  as  such  in  nature. 

The  author  therefore  advocates  that  the  words  "bitumen"  and 
"bituminous  substance"  be  defined  in  scope  as  expressed  in  View 
(a),  which  is  exactly  as  they  have  been  heretofore  used  and  accepted 
in  the  language.  He  believes  further  that  by  using  these  two  terms 
co- jointly,  a  satisfactory  system  of  classification  may  be  devised, 
which  will  answer  adequately  the  needs  of  the  scientific  fraternity, 


62 


TERMINOLOGY  AND  CLASSIFICATION 


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BITUMINOUS  SUBSTANCES 


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64  TERMINOLOGY  AND  CLASSIFICATION  II 

and  at  the  same  time  be  in  complete  harmony  with  the  dictionary 
definitions  as  they  now  exist. 

With  the  foregoing  in  mind,  the  author  has  worked  out  a  basis 
for  classifying  bituminous  substances,  including  the  most  important 
members  recognized  commercially,  which  will  be  found  in  Table  III. 


CHAPTER  III 
CHEMISTRY  OF  BITUMINOUS  SUBSTANCES 

Bituminous  substances  in  general  may  be  regarded  as  consisting 
of  one  or  more  of  the  following  components: 

(A)  The  Non-mineral  Matrix. 

(B)  Associated  Mineral  Constituents. 

(C)  Associated  Non-mineral  Constituents. 

Each  component  will  be  considered  in  turn. 

(A)  COMPOSITION  OF  NON-MINERAL  MATRIX 

The  non-mineral  matrix  present  in  bituminous  substances  is  a 
complex  mixture  of  hydrocarbons  together  with  their  sulfur  and 
nitrogen  derivatives,  and  are  frequently  associated  with  mineral 
constituents  in  varying  amounts.  The  non-mineral  constituents  are 
accordingly  composed  of  the  elements  carbon  and  hydrogen,  with 
more  or  less  sulfur,  nitrogen,  and  at  times  oxygen.  The  constituent 
hydrocarbons  may  either  be  saturated  or  unsaturated.  Saturated 
hydrocarbons  are  those  in  which  the  carbon  valence  has  been  com- 
pletely taken  up  by  hydrogen  or  other  radicals,  and  are  characterized 
by  their  resistance  to  reagents  (e.g.  acids  and  alkalies)  and  the  dif- 
ficulty with  which  they  form  substitution  compounds.  Unsaturated 
hydrocarbons  are  those  having  free  carbon  valences,  and  have  the 
property  of  forming  additive  compounds. 

Every  member  of  the  bituminous  family  is  a  homogeneous  or 
heterogeneous  mixture,  consisting  of  a  multitude  of  chemical  sub- 
stances, each  having  a  definite  molecular  composition.  These  con- 
stituent substances  may  be  associated  as  a  simple  solution  of  liquids 
in  liquids,  or  solids  in  liquids;  or  in  the  form  of  a  colloidal  solution; 
or  as  a  solid  solution  of  amorphous  or  crystalline  solids;  or  as  an 
emulsion  of  immiscible  liquids;  or  as  a  suspension  of  insoluble  sub- 
stances in  a  more  or  less  liquid  matrix;  or  combinations  of  two  or 

more  of  the  foregoing  phases. 

65 


66  CHEMISTRY  OF  BITUMINOUS  SUBSTANCES  III 

It  is  contended  that  the  characteristic  dark  color  of  asphalts  is 
due  to  the  liberation  of  colloidal  carbon  under  the  influence  of  heat, 
which  is  then  adsorbed  by  the  hydrocarbons.1  The  colloidal  nature 
of  asphalt  is  confirmed  by  the  Tyndall  effect,  the  Brownian  move- 
ment observed  under  the  ultra-microscope  even  in  dilute  solutions, 
the  fact  that  on  distillation  no  trace  of  asphaltic  or  coal-like  sub- 
stances are  found  in  the  distillate,  and  the  further  fact  that  asphal- 
tenes  retain  hydrogen  even  at  800°  F. 

F.  J.  Nellensteyn  regards  asphalt  as  a  protected  ulyophobe  sol," 
or  an  extremely  stable  ucarbon-oleosole,"  in  the  form  of  a  "system" 
consisting  of  three  components,  viz.  : 

(1)  The   "medium"    (corresponding  to  the  so-called  "petro- 
lenes"  or  "oily  constituents"). 

(2)  The  "lyophilic  portion"  or  protective  bodies  (correspond- 
ing to  the  so-called  "asphaltic  resins"). 

(3)  The  "lyophobic  portion,"  composed  of  colloidal  particles 
or  ultra-microns  of  elemental  carbon. 

An  adsorption  relation  exists  between  components  (2)  and  (3), 
forming  a  "disperse  phase"  and  constituting  the  so-called  "asphalt 
micelle"  (corresponding  to  the  "asphaltenes").  According  to  this 
hypothesis,  the  asphalt  constituents  may  be  classified  into  the  fol- 
lowing systems : 

Petrolenes  (malthenes)  and  oily  constituents  =  oily  medium. 
Asphaltous  acids  plus  asphaltous  acid  anhydrides  plus  asphaltic 

resins  =  small  amount  of  carbon  with  very  large  amount  of 

protective  bodies. 

Asphaltenes  ==  carbon  with  protective  bodies. 
Carbenes  =  carbon  with  small  amount  of  protective  bodies. 
Pyrobitumens  =  carbon  with  very  little  protective  bodies. 

The  stability  of  the  "system"  depends  upon  the  respective  sur- 
face tensions  of  the  "medium"  and  "micelle."  Changes  in  the  sta- 
bility, including  "flocculative"  and  "peptizing"  reactions,  give  rise  to 
a  "reversible  flocculation."  If,  however,  the  micelle  itself  is  de- 
stroyed and  cannot  be  directly  repeptized,  the  substance  is  said  to 
have  undergone  an  "irreversible  flocculation."  The  latter  is  caused 
by  chemical  reactions  (e.g.  iodine,  chlorine,  etc.) ;  by  heat;  or  by 
exhaustive  extraction  of  asphaltenes  with  different  solvents  of  suc- 
cessively higher  surface-tension.  In  natural  asphalts  associated  with 


Ill 


(A)  COMPOSITION  OF  NON-MINERAL  MATRIX 


67 


colloidal  mineral  matter  (e.g.  Trinidad  asphalt),  the  ultra-microns 
present  in  the  micelle  consist  partly  of  elemental  carbon  and  partly 
of  inorganic  material.  Adding  finely  divided  fillers  to  asphalt  may 
result  in  the  formation  of  such  micelles. 

The  properties  of  asphalts  depend  upon  the  concentration  of  the 
disperse  phase,  its  degree  of  subdivision,  as  well  as  the  properties  of 
the  medium.  The  combination  of  these  functions  leads  from  the 
crude  petroleum,  through  the  soft  and  viscous  asphalts,  over  to  the 
asphaltites.  For  the  mechanism  of  this  col- 
loidal system  in  its  transition  from  petro- 
leum to  the  hard  asphalts  and  asphaltites, 
the  following  theory  may  be  developed,  in 
which  the  underlying  idea  is  clearly  illus- 
trated. In  Fig.  24  the  black  points  and 
areas  represent  the  "asphalt  micelles,"  the 
white  points  and  areas  the  "oily  medium." 
In  region  A,  the  asphalt  micelles  are  pres- 
ent in  such  slight  amount  and  in  such  a  high 
degree  of  subdivision  that  they  exist  in  the 
oily  medium  in  the  form  of  a  molecularly 
dispersed  solution.  This  region  corre- 
sponds to  the  characteristics  of  crude  petro- 
leum before  it  is  subjected  to  distillation 
in  the  preparation  of  residual  asphalt. 
In  the  distillation  process,  the  concen- 
tration of  the  oily  medium  gradually 
diminishes,  and  the  particle  size  of  the 
dispersed  phase  (asphalt  micelles)  cor- 
respondingly increases,  until  they  assume 
a  dimension  larger  than  molecular,  and 


FIG.  24. — Formation  of  As- 
phalts Illustrated  Diagram- 
matical ly. 


eventually  reach  the 
state  of  a  colloidal  dispersion.  The  gradual  enlargement  of  the 
micelles,  or  the  increase  in  their  number  (through  continued  distil- 
lation) is  illustrated  by  regions  B,  C,  D  and  E,  which  represent  the 
disperse  systems  of  soft  to  moderately  hard  asphalts.  Further  re- 
duction of  the  oily  phase  causes  constantly  greater  reduction  of  the 
distances  of  the  micelles  from  one  another,  and  accordingly  leads  to 
the  agglomeration  of  the  asphalt  micelles,  as  shown  in  region  F. 
We  then  come  into  the  range  of  hard  asphalts  and  the  reversal  of 


68  CHEMISTRY  OF  BITUMINOUS  SUBSTANCES  III 

phases.  If  the  reduction  of  the  oily  medium  continues  further,  then 
the  aggregates  of  the  micelles  become  so  large  and  their  number  in- 
creases to  a  degree  that  they  eventually  fuse  together,  resulting  in 
the  asphalt  micelles  forming  the  continuous  phase  and  the  oily  con- 
stituents the  disperse  phase,  as  illustrated  in  regions  V,  W,  X  and  Y. 
If  the  process  continues  sufficiently  far,  the  system  will  finally  consist 
only  of  asphalt  micelles,  as  shown  in  region  Z.  Regions  V  to  Z  em- 
brace the  hard,  high  fusing-point  asphalts  and  asphaltites. 

It  is  a  comparatively  simple  matter  to  ascertain  by  analytical 
methods  the  percentage  by  weight  of  the  elements  present.  This  is 
termed  the  ultimate  analysis,  in  contra-distiriction  to  the  molecular 
composition. 

The  greatest  percentage  of  carbon  found  in  any  bituminous  sub- 
stance is  in  the  case  of  anthracite  coal,  which  runs  as  high  as  98 
per  cent  The  smallest  percentage  is  contained  in  certain  peats, 
which  run  as  low  as  50  per  cent.  With  the  exception  of  the  non- 
asphaltic  pyrobitumens,  carbon  ranges  from  85  to  95  per  cent. 

Hydrogen  never  exceeds  15  per  cent.  In  the  paraffin  series  of 
hydrocarbons,  the  carbon  is  combined  with  as  much  hydrogen  as 
possible,  and  this  accordingly  contains  the  largest  percentage  of 
hydrogen  and  the  smallest  percentage  of  carbon.  The  lowest  mem- 
ber of  this  series  CtL,  a  gas,  contains  75  per  cent  of  carbon  and  25 
per  cent  of  hydrogen.  The  member  C3oHe2  contains  85.31  per  cent 
of  carbon  and  14.69  per  cent  of  hydrogen.  In  the  olefin  series 
CnHU,  the  relation  of  carbon  to  hydrogen  is  constant,  and  figures : 
carbon  85.71  per  cent  and  hydrogen  14.29  per  cent. 

The  percentage  of  sulfur  varies  considerably.  Waxes,  coal  tar 
and  coal-tar  pitch,  pine  tar  arid  pine-tar  pitch,  hardwood  tar  and 
hardwood-tar  pitch,  also  fatty-acid  pitch  are  practically  free  from 
sulfur.  In  petroleum,  the  sulfur  varies  from  a  trace  to  5  per  cent 
as  a  maximum.  Mexican  petroleum  contains  between  3  and  5  per 
cent;  Trinidad,  Venezuela  and  California  petroleums  contain  be- 
tween l/2  and  4  per  cent;  semi-asphaltic  petroleums  including  the 
Mid-continental  and  Texas  oils  contain  from  a  trace  to  2]/2  per  cent 
Paraffinaceous  petroleums  contain  merely  a  trace.  Residual  oils 
contain  from  a  trace  to  5  per  cent.  Residual  asphalts,  blown  as- 
phalts, sludge  asphalts,  native  asphalts,  asphaltites,  asphaltic  pyro- 
bitumens and  non-asphaltic  pyrobitumens  contain  from  a  trace  to  ifr 


Ill  (A)  COMPOSITION  OF  NON-MINERAL  MATRIX  69 

per  cent  sulfur.  Tars  and  pitches  derived  from  non-asphaltic  pyro- 
bitumens  contain  from  a  trace  to  I J4  per  cent 

Nitrogen  is  rarely  present  in  excess  of  2  per  cent.  Mineral 
waxes  are  free  from  nitrogen.  Petroleum  asphalt,  asphaltites  and 
pyrobitumens  contain  from  a  trace  to  1.7  per  cent  nitrogen.  Tars 
and  pitches  contain  from  o  to  I  per  cent. 

Oxygen  rarely  exceeds  5  per  cent,  except  in  the  case  of  non- 
asphaltic  pyrobitumens  which  contain  up  to  45  per  cent  of  oxygen. 

At  the  present  time  but  a  comparatively  small  number  of  dis- 
tinct chemical  substances  have  been  identified  in  bituminous  com- 
plexes. A  vast  amount  of  research  work  must  yet  be  accomplished. 
Although  hundreds  of  substances  of  definite  molecular  composition 
have  been  identified  in  petroleums,  native  mineral  waxes,  pyrogenous 
waxes  and  certain  tars,  comparatively  little  is  known  regarding  the 
innumerable  non-mineral  molecular  substances  present  in  native  as- 
phalts, asphaltites,  asphaltic  pyrobitumens,  non-asphaltic  pyrobitu- 
mens, pyrogenous  asphalts  and  pitches. 

The  chemistry  of  bituminous  substances  is  further  complicated 
by  the  fact  that  commercial  specimens  of  any  given  material  are 
rarely  alike  in  composition.  In  some,  certain  chemical  bodies  pre- 
dominate ;  in  others,  they  may  be  present  in  smaller  amounts ;  while 
in  still  others  they  may  be  absent.  Thus  two  shipments  of  any 
given  member  of  the  bituminous  family  are  apt  to  fluctuate  widely 
in  composition  and  physical  properties,  even  when  emanating  from 
the  same  source.  Again,  a  native  bituminous  substance  derived 
from  a  single  deposit  will  often  vary,  depending  upon  the  degree  of 
exposure  and  extent  of  metamorphosis.  Native  bituminous  sub- 
stances are  in  a  constant  state  of  transition,  as  the  result  of  their 
age  and  environment.  Pyrogenous  bituminous  substances  show  a 
marked  variation  in  composition  and  physical  properties,  depending 
upon  the  raw  materials  used  in  their  production  and  the  exact  con- 
ditions to  which  they  have  been  subjected  in  their  processes  of  manu- 
facture, including  the  temperature,  length  of  treatment,  etc.  Bitu- 
minous substances  should  not  therefore  be  compared  with  vegetable 
or  animal  fats  or  oils,  which  in  the  case  of  any  given  material  will 
run  fairly  uniform  in  composition  and  physical  properties. 

In  certain  instances,  comparatively  simple  tests  have  been  de- 
vised for  identifying  single  chemical  bodies  present,  whereas  in  other 


70  CHEM1STR?  OF  BITUMINOUS  SUBSTANCES  III 

cases  the  ultimate  analysis  of  the  material  will  furnish  a  clue  to  the 
identity  of  the  substance  under  examination. 

Various  methods  have  been  proposed  to  separate  bituminous 
substances  into  their  constituents,  including  fractional  distillation 
under  reduced  pressure,2  the  selective  action  of  solvents,3  the  use  of 
adsorption  media,4  and  combinations  of  the  foregoing. 

(B)  COMPOSITION  OF  ASSOCIATED  MINERAL  CONSTITUENTS 

The  mineral  constituents  may  be  present  in  one  or  more  of  the 
following  typical  forms : 

1.  As  consolidated  mineral  particles  consisting  of  a  porous  rock 
impregnated  with  the  bituminous  constituents.  This  type  is  exem- 
plified by  the  so-called  urock  asphalts,"  which  are  usually  composed 
of  a  fine-grained  limestone  or  sandstone  matrix,  carrying  the  asphalt 
in  its  voids. 

2.  As  unconsolidated  mineral  particles  admixed  mechanically 
with  the  bituminous  constituents.    This  is  typified  by  the  numerous 
deposits  of  impure  native  asphalts  and  asphaltites,  in  which  the 
bituminous  constituents  are  associated  with  more  or  less  detritus 
derived  from  the  surrounding  soil ;  also  blast-furnace  tar  and  pitch 
which  carry  a  proportion  of  mineral  dust  carried  over  mechanically 
by  the  furnace  gases  as  well  as  metallic  compounds  which  result  from 
the   corrosion  of  pipe  lines   and  containers  used  in  storage   and 

transport. 

The  principal  unconsolidated  mineral  constituents  present  in  na- 
tive asphalts  and  asphaltites  consist  of  calcium  carbonate,  magnesium 
carbonate,  calcium  sulfate,  dolomite,  clay,  silica  and  the  various 
silicates,  iron  sulfide,  etc. 

3.  As  colloidal  mineral  particles  held  in  suspension  by  the  bitu- 
minous constituents.    Trinidad  Lake  asphalt  is  typical  of  this  group, 
and  is  characterized  by  the  presence  of  colloidal  clay  and  silica 
which  are  not  removable  by  filtration  and  are^  readily  discernible 
when  viewed  under   an  ultra-microscope.5     Richardson   makes  a 
special  virtue  of  the  fact  that  refined  Trinidad  asphalt  contains  nat- 
urally about  27  per  cent  filler  composed  largely  of   "colloidal" 
particles. 

4.  As  mineral  matter  held  in  chemical  combination  by  the  non- 
mineral   (i.e.,  pure  bituminous)   constituents.     This  group  differs 
from  the  foregoing,  inasmuch  as  it  relates  to  a  chemical  union  of  the 
mineral  and  non-mineral  components.     Many  native  asphalts  carry 
small  percentages  of  iron  and  aluminium,  but  it  is  as  yet  a  mooted 
question  whether  these  are  present  as  colloidal  particles,  or  united 


Ill  (C)  ASSOCIATED  NON-MINERAL  CONSTITUENTS  71 

chemically  with  the  bituminous  matter.  Most  residual  and  blown 
petroleum  asphalts  contain  a  trace  of  iron,  derived  from  the  stills  in 
which  they  are  refined.  Fatty-acid  pitch,  wood-tar  pitch,  bone-tar 
pitch  and  rosin  pitch  carry  a  substantial  amount  of  iron  or  copper, 
depending  upon  whether  they  have  been  produced  in  an  iron  or 
copper  still.  Sludge  asphalts  bear  a  trace  of  combined  lead  derived 
from  the  lead  containers  in  which  they  have  been  treated. 

Rare  elements  are  also  normally  associated  with  certain  native 
asphalts  and  asphaltites.  Thus  the  following  proportions  of  nickel, 
expressed  in  parts  per  million,  have  been  reported : 6  Trinidad  as- 
phalt 194,  Swiss  asphalt  120,  gilsonite  133,  residual  asphalt  from 
U.  S.  petroleum  240,  crude  U.  S.  petroleums  i  to  93  parts,  ozokerite 
trace  to  nil.  Vanadium  is  present  in  most  varieties  of  petroleum  and 
asphalt,7  and  has  also  been  reported  in  Argentine  grahamite  8  and 
Peruvian  impsonite.9  Vanadium  occurs  in  the  more  asphaltic  crudes, 
but  is  not  present  in  any  quantity  in  non-asphaltic  (i.e.,  paraffin- 
aceous)  crudes.  A  high  vanadium  content  is  generally  associated 
with  a  high  nickel  content.10  Uranium  has  similarly  been  reported 
in  glance  pitch  found  in  Utah,11  and  molybdenum  in  asphaltic  petro- 
leum 12  and  Holzheim  (Swabian)  oil  shales. 


(C)  COMPOSITION  OF  ASSOCIATED  NON-MINERAL 
CONSTITUENTS 

Native  asphalts  often  contain  non-mineral  impurities  in  the  form 
of  decayed  vegetable  substances  of  peat-like  nature,  which  were 
originally  present  in  the  soil,  now  associated  with  the  asphalt.  These 
substances  are  derivatives  of  humic,  or  ulmic,  crenic,  etc.,  acids. 

Certain  tars  and  pitches  as  well  as  residual  asphalts,  which  have 
been  overheated  in  their  process  of  manufacture,  will  carry  variable 
amounts  of  so-called  ufree  carbon."  This  in  reality  consists  of 
hydrocarbon  derivatives,  polymerized  under  the  influence  of  heat 
to  an  insoluble  modification,  similar  in  certain  respects  to  bitumi- 
nous coal.  It  is  probable  that  the  "free  carbon"  may  under  certain 
conditions  consist  in  part  of  amorphous  carbon,  similar  to  lamp- 
black. R.  Hodurek  has  demonstrated  that  tars  inherently  contain 
certain  insoluble  constituents  which  may  be  removed  by  filtration 
(which  he  designates  "Carbon  I")  and  that  other  substances  ("Car- 
bon II")  are  formed  by  precipitation  upon  dissolving  the  tar  in 
solvents,  the  quantity  being  dependent  upon  the  particular  solvent 
employed.14 


72  CHEMISTRY  OF  BITUMINOUS  SUBSTANCES  III 

(D)  BEHAVIOR  WITH  SOLVENTS 

This  question  will  be  taken  up  in  detail  in  Chapter  XXVI. 
(E)  BEHAVIOR  ON  SUBJECTING  TO  HEAT 

On  heating  bitumens,  the  following  reactions  take  place :  at  low 
temperatures  they  commence  to  distil  without  decomposition.  Con- 
tinued heating  causes  a  rapid  change  in  penetration  and  viscosity 
during  the  first  few  days  or  weeks,  whereas  the  flash-point  is  least 
affected.  The  fusing-point  changes  regularly  but  markedly.  There 
is  a  general  decrease  in  acidity  (i.e.,  acid  value)  which  finally  attains 
a  constant  figure.16  As  the  temperature  increases,  a  certain  amount 
of  cracking  takes  place,  resulting  in  the  depolymerization  of  both  the 
distillate  and  residue.  At  still  higher  temperatures,  the  distillate 
continues  to  deploymerize,  whereas  the  residue  commences  to  polym- 
erize with  the  formation  of  asphalt-like  bodies.  Beyond  this,  the 
residue  again  undergoes  depolymerization  with  the  evolution  of  a 
certain  amount  of  fixed  gases,  likewise  the  formation  of  carbenes, 
free  carbon,  and  eventually  elemental  carbon.  Thus  in  the  case  of 
non-asphaltic  and  semi-asphaltic  petroleums,  polymerization  takes 
place  when  the  residue  in  the  still  reaches  600  to  800°  F.,  whereby 
asphalt-like  substances  are  produced.  In  other  words  the  percentage 
of  asphalt  in  petroleum  is  actually  increased  under  these  conditions. 
Beyond  this  temperature,  cracking  takes  place,  in  which  the  asphalt 
is  destructively  distilled  and  decomposed  into  simpler  molecules, 
yielding  gases,  liquid  distillates  and  a  residue  of  coke.16 

The  asphaltic  pyrobitumens  behave  differently.  When  heated 
to  between  600  and  800°  F.,  they  undergo  "cracking."  This  is  in 
reality  a  form  of  depolymerization  in  which  complex  molecules  are 
broken  down  into  simpler  ones.  As  a  result,  the  original  substance, 
which  is  practically  insoluble  in  organic  solvents,  increases  materially 
in!  solubility.  Elaterite  and  wurtzilite  depolymerize  and  become 
completely  soluble  in  benzol  and  carbon  disulfide.  Albertite  is  more 
difficult  to  depolymerize  than  elaterite  or  wurtzilite,  requiring  a 
higher  temperature  and  an  increased  time  of  treatment.  On  the 
other  hand,  impsonite  depolymerizes  only  slightly  under  these  con- 
ditions. If  heated  to  higher  temperatures,  the  asphaltic  pyrobitu- 
mens suffer  destructive  distillation,  leaving  a  residue  of  coke.  The 
depolymerization  is  similar  to  the  action  which  takes  place  on  melt- 


Ill 


(E)   BEHAVIOR   ON  SUBJECTING   TO  HEAT 


73 


ing  fossil  resins,  such  as  copal,  amber,  etc.,  in  manufacturing  varnish. 
A  schematic  outline  of  what  occurs  upon  subjecting  bitumens  and 
pyrobitumens  to  heat  is  given  in  the  following  tabulation : 


TABLE  IV 
BEHAVIOR  ON  SUBJECTING  TO  HEAT 


Heated 
under  300°  C. 

Heated 
300-450°  C. 

Heated 
450-700°  C. 

Heated 
700-1500°  C. 

Non-asphaltic 

Distil  and  the 

Residues     de- 

petroleums 

residues  fuse 

polymerize 

slightly 

S  e  mi-  asphalt!  c 

Distil  and  the 

Residues  poly- 

and asphaltic 

residues  fuse 

merize,  form- 

petroleums 

ing    asphalt- 

like  bodies 

Depolymerize, 

Bitumens 

Mineral  waxes 

Small  amount 

Depolymerize 

yielding    as 

distils   with 

and  distil 

distillate 

slight  decom- 

mostly open- 

position,  and 

•     chain   hy- 

the  residues 

drocarbons 

fuse 

and  a  resi- 

Asphalts and 

Fuse 

Distil  more  or 

due  of  coke 

Asphaltites 

less 

Asphaltic  pyro- 

Infusible  and 

Depolymerize 

bitumens 

insoluble 

and  become 

Pyrobitumens.  .  ' 

Non-asphaltic 

Infusible 

more  soluble 
Unaffected 

Depolymerize 

Depolymerize, 

pyrobitumens 

slightly    and 

yielding    as 

distil 

distillate, 

mostly  cyclic 

hydrocarbons 

and  a  residue 

of  coke 

F.  J.  Nellensteyn  has  proposed  the  following  theory  to  account 
for  the  formation  of  asphalts  and  the  like: 

(/)   Formation  of  Asphalts: 
Hydrocarbons  {$$*  }  = 

Transformed  to  carbon  +  Adsorbed  protective  hydrocarbon  bodies 

Asphaltenes 

(//)   Behavior  of  the  Asphaltenes: 


Asphaltenes 


extracted 

oxidized 

heated 


74  CHEMISTRY  OF  BITUMINOUS  SUBSTANCES  III 

Carbon  +  Small  amount  of  adsorbed  protective  hydrocarbon  bodies 

Free  carbon 

Free  carbon      { heated     }  = 

Carbon  +  Very  small  amount  of  adsorbed  hydrocarbon  bodies 

Retort  carbon 

Resulting  in  a  further  decomposition  of  the  protective  bodies. 

(///)   Synthesis  of  Asphaltenes: 
Retort  carbon  {electrically  atomized  in  the  presence 
of  protective  hydrocarbon  bodies  }  = 

Carbon  +  Adsorbed  protective  hydrocarbons 
Asphaltenes 

(F)  REACTIONS  WITH  GASES 

(a)  Oxygenation.     On  blowing  air  through  bituminous  sub- 
stances at  fairly  high  temperatures,  hydrogen  is  removed  in  the  form 
of  water,  and  at  the  same  time  the  hydrocarbons  polymerize,  form- 
ing bodies  of  higher  molecular  weight  and  more  complex  structure. 
The  reaction  may  be  roughly  represented  as  follows : 

CxHy  +  O  =  CxHy_2  +  H2O 

Analysis  shows  that  little  or  no  oxygen  actually  combines  with 
the  asphalt.17  One  theory  is  that  polyhydric  compounds  acidic  in 
character,  are  formed  during  the  intermediate  stage  of  oxidation, 
which  upon  further  heating  change  to  anhydrides  similar  to  the  poly- 
naphthenic  acids,  with  progressive  condensation  and  polymerization. 
Various  bituminous  substances  are  affected  differently  by  the  blowing 
process.  Asphalts  present  in  petroleum  are  readily  converted  into, 
tough,  rubber-like  products  having  a  higher  fusing-point  and  much 
more  resistant  to  temperature  changes.  Fatty-acid  pitch  behaves  in 
a  similar  manner.  Natural  asphalts  are  affected  very  much  less, 
and  pitches  derived  from  coal  and  wood  are  scarcely  affected  at  all. 
Even  the  petroleum  asphalts  themselves  are  affected  differently,  de- 
pending upon  their  origin  and  chemical  characteristics.  This  sub- 
ject will  be  gone  into  more  fully  under  the  heading  44Petroleum 
Asphalts." 

(b)  Hydrogenation.    This  is  carried  out  by  heating  bituminous 
substances  (e.g.,  coal,  asphalt,  paraffin  wax,  tars,  etc.)  with  hydro- 


Ill  (F)  REACTIONS  WITH  GASES  75 

gen  in  an  autoclave  at  high  pressures  (100  to  200  atmospheres)  at 
400  to  450°  C.  The  process  was  discovered  by  Friedrich  Bergius,18 
and  has  been  termed  "berginization."  The  following  changes  take 
place : 

1 i )  Thermal  decomposition,  i.e.,  cracking. 

(2)  Hydrogenation,  whereby  the  unsaturated  hydrocarbons  re- 
sulting from  the  thermal  decomposition,  at  their  moment  of  forma- 
tion, react  with  the  hydrogen,  producing  saturated  hydrocarbons  of 
lower  boiling-points. 

The  process  differs  from  straight  thermal  decomposition  in  the 
following  respects:  extensive  polymerization  is  avoided  and  the 
deposition  of  carbonaceous  matter  is  almost  entirely  prevented, 
moreover,  as  the  reaction  proceeds  the  pressure  in  the  autoclave 
falls,  due  to  the  absorption  of  hydrogen,  whereas  in  the  absence  of 
hydrogen,  the  pressure  would  increase  due  to  the  formation  of  fixed 
gases.  Finally,  the  end  product  consists  largely  of  saturated  hydro- 
carbons, whereas  in  the  cracking  processes,  unsaturated  bodies  will 
predominate.  The  resulting  products  are  characterized  by  a  higher 
hydrogen  content.  Any  oxygen  present  in  the  original  material  is 
converted  into  water,  and  any  nitrogen  into  ammonia. 

In  treating  petroleum  by  the  Bergius  hydrogenation  process,  hy- 
drogen gas  is  introduced  at  a  pressure  of  about  3600  Ibs.  per  sq.  in. 
in  the  presence  of  a  catalyst.  Molybdic  anhydride  and  sulfur  19 
seems  to  be  most  favored,  although  numerous  othef  catalyzers  have 
been  proposed,  including  chromium,  tungsten,  uranium,  manganese, 
cobalt,  etc.,  compounds,  also  metallic  iron  or  nickel.20  The  catalyst 
should  be  sulfur-resistant  and  serve  to  speed  up  the  reaction  and 
eliminate  the  oxygen  from  the  hydrogenated  product.  Relatively 
impure  hydrogen,  containing  hydrogen  sulfide,  is  used,  produced 
from  coal  or  coke  by  the  water-gas  process. 

Asphaltic  crudes  of  all  characters  (e.g.,  Venezuelan,  Panuco,  Co- 
lombian, etc.),  likewise  residues  from  refinery  crudes,  as  well  as 
cracking-plant  tars,  may  be  converted  into  volatile  distillates,  free 
from  asphalt  and  low  in  sulfur,  with  volumetric  yields  somewhat  in 
excess  of  100%  (although  the  specific  gravity  of  the  product  is 
usually  less  than  the  crude  stock).  Dark  asphaltic  constituents  are 
converted  into  practically  colorless  hydrocarbons  of  the  gasoline 
range.  In  other  words,  the  hydrogen  will  combine  with  the  colloidal 


76 


CHEMISTRY  OF  BITUMINOUS  SUBSTANCES 


III 


carbon  present  in  the  asphalt  present.  In  actual  practice,  the  petro- 
leum is  first  topped  to  remove  all  the  gasoline  present.  From  mixed- 
base  crudes,  highly  paraffinic  products  may  be  produced,  such  as 
gas-oils,  burning  oils  and  high-grade  lubricants.  From  paraffin 
crudes,  so-called  aromatic  products  may  be  produced,  as  for  example, 
a  highly  anti-knock  gasoline.  No  coke  is  produced  in  the  process. 

The  charging  stock,  together  with  sufficient  hydrogen,  is  pumped 
through  heat-exchangers  to  a  coil-furnace,  and  thence  into  the  reac- 
tion vessel  containing  the  catalyst  where  it  is  subjected  to  the  re- 
quired temperature  and  pressure.  Units  have  been  installed  capable 
of  treating  5000  barrels  of  crude  daily.21  The  final  products  with 
the  gases  pass  through  heat-exchangers  and  coolers  to  a  high-pres- 
sure separator,  where  the  liquid  reaction  products  are  separated 
from  the  unconsumed  hydrogen  and  other  gases,  which  latter  are 
scrubbed  with  oil  under  pressure  to  remove  the  hydrogen  sulfide, 
and  the  purified  gas  used  over  again. 

The  following  five  adaptations  of  hydrogenation  appear  to  be  of 
most  importance  in  petroleum  refining: 22 

TABLE  V 


APPROXIMATE  VOLUMETRIC 

YIELD  or 

TOTAL 

GAS 

PROCESS 

CHARGING  STOCK 

PRIMARY  RESUI-T 

VOLU- 

FORMA- 

Gasoline 

Burn- 
ing Oil 

Gas 
Oil 

Lube 
Oil 

METRIC 
YIELD 

TION 

% 

% 

% 

% 

% 

%byvt. 

z 

High-sulfur,  asphalt- 

Asphalt  and  sulfur  elimination 

ic  heavy  residue 

with  simultaneous  conversion 

entire  charge  into  distillate 

oils 

30 

71 

.  .  . 

zoz 

2  to  3 

a 

Low-grade  lube  dis- 

Production premium  lube,  par- 

tillate 

ticularly  as  regards  temper- 

ature-viscosity   relationship, 

flash,  carbon,  and  gravity 

10 

.... 

29 

6S 

Z04 

0.5  to  z,s 

3 

Low-grade   burning 

Production  of  low-sulfur  pre- 

oil distillate 

mium  grade  burning  oil 

3Q 

73 

zo3 

O-S  tO  2 

4 

Cracked  naphtha 

Desulfurization  and  gum  sta- 

,' 

bilization  without  deteriora- 

tion in  yield  and  knock  rating 

characteristic  of  acid  treating 

zoo 

.... 

.  .  . 

zoo 

0.5 

.5 

Paraffinic  gas  oil 

Production  of  low-sulfur,  low- 

gum,  good  antiknock  gasoline 

65  to  zoo 

70  to  zoo 

S  to  35 

If  the  charging  stock  is  paraffinic  in  character,  it  is  heated  to 
750°  F.,  and  if  aromatic,  to  1000°  F.  The  reaction  is  exothermic.23 
It  is'  advocated  that  very  heavy  asphaltic  crudes  be  treated  in  three 


Ill  (£)  REACTIONS  WITH  ACIDS  77 

stages,  at  pressures  of  1000,  200  and  20  atmospheres,  respectively*04, 
The  residual  product  obtained  from  the  hydrogenation  of  residual 
asphalts  has  characteristics  somewhat  similar  to  those  of  blown  pe- 
troleum asphalt.25  Partial  hydrogenation  of  petroleum  stocks  at 
900  to  950°  F.,  without  using  a  catalyst,  is  claimed  to  result  in  the 
precipitation  of  any  asphalt  present26  Low-temperature  coal-tar 
(topped  to  200°  C.),  when  hydrogenated  with  a  mixture  of  molybdic 
acid  and  sulfur  as  catalyst,  under  an  initial  pressure  of  145  atmos- 
pheres, yielded  99.2%  of  hydrogenated  oil.  The  reaction  started 
at  200°  C.,  which  increases  to  a  maximum  of  360°  C.27  The  prod- 
uct is  free  from  tar  acids  and  pitchy  matters.28  Cdke-oven  tar 
showed  an  increase  in  volatile  products  below  300°  C.  from  31.7 
to  65.5%,  and  in  this  case  the  hydrogen  was  absorbed  by  the  liquid 
residue  as  well  as  by  the  fixed  gases.  Paraffin  wax  was  entirely  con- 
verted into  liquid  and  gaseous  products.  Similarly,  Alberta  san^ 
asphalt  has  been  hydrogenated  under  a  pressure  of  1470  Ibs.  at 
380  to  410°  C.  in  the  presence  of  ammonium  molybdate  and  alumi- 
num chloride,  or  NiCOs  and  Fe2O8  or  CaO  (to  remove  the  sulfur), 
being  converted  into  80  to  90%  by  weight  of  oils  based  on  the  as-? 
phalt  present  in  the  raw  material,  and  involving  the  absorption  of 

by  weight  of  hydrogen.29 

A  modification  of  the  preceding  has  been  devised  by  Meilach 
Melamid,  which  consists  in  atomizing  asphaltic  petroleum  into  a 
heated  reaction  chamber  together  with  hydrogen,  so  that  the  two 
are  brought  in  contact  with  a  catalyzer  (e.g.,  tin  or  bismuth  alloys 
melting  below  700°  F.)-80  In  this  process  the  hydrogenation  and 
continuous  distillation  of  the  crude  oil  take  place  simultaneously. 
In  the  case  of  a  Panuco  (Mexican)  crude,  the  distillate  to  320°  C. 
was  increased  from  19  to  26  per  cent,  and  in  the  case  of  a  brown-* 
coal  tar  resulting  from  the  Mond  gas  process,  the  pitch  residue  was! 
reduced  from  46.8  per  cent  to  o.o  per  cent,  with  a  corresponding 
increase  in  the  percentages  of  distillates. 

(G)  REACTIONS  WITH  ACIDS 

(a)  Liquid  Sulfur  Dioxide*  This  agent  has  the  property  of 
dissolving  unsaturated  hydrocarbons  ait  low  temperatures  ( — •  7°  to 
—  11°  F.),  whereas  the  saturated  hydrocarbons  remain  substan- 


78  CHEMISTRY  OF  BITUMINOUS  SUBSTANCES  III 

tially  insoluble.  Advantage  is  taken  of  this  fact  in  certain  commer- 
cial refining  operations,  also  in  the  laboratory  examination  of  bitu- 
minous substances.81  In  general,  the  higher  boiling-point  paraffins, 
naphthenes  and  naphthenic  acids  (i.e.,  over  175°  C.)  are  insoluble, 
whereas  the  aromatics  and  the  true  unsaturated  hydrocarbons  (con- 
taining two  or  more  double  bonds)  are  miscible  with  liquid  sulfur 
dioxide  in  all  proportions.  Sulfur  and  its  organic  combinations, 
nitrogen  compounds,  resinous  and  asphaltic  substances  are  also  sol- 
uble, though  their  solubilities  decrease  with  increasing  complexity  of 
the  molecule.82 

(b)  Sulfuric  Acid  and  Sulfur  Trioxide.     Concentrated  sulfuric 
acid,  or  a  mixture  of  concentrated  sulfuric  acid  with  sulfur  trioxide 
reacts  with  bituminous  substances  in  a  somewhat  complicated  man- 
ner, involving  both  the  formation  of  sulfo  derivatives  and  that  of 
simple  solution,  accompanied  by  a  certain  amount  of  polymeriza- 
tion.    In  general,  it  may  be  stated  that  the  following  classes  of 
substances  are  removed  by  concentrated  sulfuric  acid:  unsaturated 
and  aromatic  hydrocarbons,  asphaltic  bodies,  saponifiable  constitu- 
ents and  alkaline  bases.    This  reaction  forms  the  basis  of  the  method 
used  commercially  for  refining  petroleum  distillates  and  is  likewise 
used  in  the  laboratory  under  accurately  controlled  conditions  for 
the  separation  of  saturated  and  unsaturated  hydrocarbons.     (See 
Test  34.)     A  process  has  been  described  which  consists  in  heating 
residual  asphalt  with  20  to  25  per  cent  of  concentrated  sulfuric 
acid  to  120°  C.  which  is  then  gradually  increased  to  240°  C.    The 
addition  compounds  are  separated  and  the  residue  (i.e.,  sludge  as- 
phalt) used  for  molding  purposes.33 

(c)  Nitric  Acid.     Strong  nitric  acid  reacts  in  two  ways,  namely 
in  the  formation  of  nitro  derivatives  and  in  the  oxidation  of  the 
hydrocarbons.     Which  of  these  predominates  depends  upon  the 
nature  of  the  hydrocarbons,  the  strength  of  the  acid,  the  tempera- 
ture, etc.    Although  much  work  has  been  done  in  investigating  the 
character  of  end-products,  but  little  commercial  use  has  been  made 
of  this  reaction.84    Similar  products  are  obtained  by  heating  tars, 
pitches  or  asphalt  with  substances  containing  NOa  or  NOs  radicals.35 
It  has  been  noted  that  certain  of  the  nitro  addition  products  are 
soluble  in  acetone  and  alcohol,  thus  differing  from  the  hydrocarbons 
from  which  they  were  derived. 


Ill  (/)  REACTIONS  WITH  METALLOIDS  71) 

(d)  Sulfuric  Acid  and  Formaldehyde.     Formaldehyde  in  the 
presence  of  concentrated  sulfuric  acid  reacts  with  unsaturated  cyclic 
hydrocarbons  and  asphaltic  constituents  with  the  formation  of  an 
insoluble  formolite,  whereas  the  other  classes  of  bodies  remain 
unaffected.    This  reaction  is  utilized  in  the  laboratory  examination 
of  bituminous  substances.     (See  Test  35.)     It  has  also  been  pro- 
posed to  incorporate  the  formolite  with  asphalts,  pitches,  etc.,  to 
produce  molded  products,  electrical  insulation,  etc.86 

(e)  Phosphoric  Acid.     Phosphoric  acid  has  been  proposed  for 
refining  mineral  oils,  yielding  "sludge  asphalt" 


37 


(H)  REACTION  WITH  ALKALIES 

Strong  alkalies  react  with  the  saponifiable  constituents  present, 
including  the  following  groups  of  substances :  free  asphaltous  acids, 
asphaltous  acid  anhydrides,  fatty  and  resinous  constituents.  The 
saponifiable  constituents  in  commercial  bituminous  substances  vary 
from  a  trace  in  the  case  of  bitumens  and  asphaltic  pyrobitumens, 
to  as  high  as  90  per  cent  and  over  in  the  case  of  rosin  pitch  and 
fatty-acid  pitch.  The  effects  of  alkalies  will  be  considered  later  in 
greater  detail. 

(I)  REACTIONS  WITH  METALLOIDS 

(a)  Sulfur  and  Sulfur  Bichloride.  Under  the  influence  of 
heat,  sulfur  has  the  same  condensing  effect  upon  bituminous  sub- 
stances as  oxygen,  since  it  results  in  the  removal  of  hydrogen,  but 
in  this  instance  in  the  form  of  gaseous  hydrogen  sulfide.  The  reac- 
tion may  roughly  be  represented  as  follows : 

CxHy  +  S  =   CxHy-2   +  H2S 

A  certain  amount  of  polymerization  also  takes  place,  and  where  the 
sulfur  is  used  in  excess,  it  is  likely  that  a  certain  amount  remains  in 
combination  with  the  bituminous  substances  in  the  form  of  addition 
products.  The  process  has  been  termed  "vulcanization,"  and  is 
used  to  improve  the  stability  of  bituminous  mixtures.  This  will  be 
:onsidered  more  fully  under  the  description  of  the  respective  sub- 
stances in  subsequent  chapters. 

Sulfur  dichloride  combines  with  bituminous  substances  under 


&)  CHEMISTRY  Of  BITUMINOUS  SUBSTANCES  III 

moderate  heat,  with  the  liberation  of  hydrochloric  acid  as  a  product 
of  the  reaction,  Which  may  be  roughly  indicated  by  the  following: 


=  GHy_6  +  2H*S  +  2HC1 


.  38 


This  reaction  is  merely  of  academic  interest3 

(b)  Selenium.    Selenium  combines  with  asphalts,  etc.,  at  160  to 
300°  C.  in  a  manner  analogous  to  sulfur,  with  the  liberation  of 
hydrogen  selenide,  a  proportion  of  the  selenium  remaining  in  com- 
bination with  the  residue.30 

(c)  Phosphorus.    It  has  been  noted  that  phosphorus,  or  PgOs 
under  the  influence  of  moderate  heat,  will  cause  asphalts  to  polym- 
erize, and  in  part  combine  chemically  with  the  asphalt,  resulting 
in  an  increase  of  hardness,  fusing-point  and  stability.40 

(d)  Halogens.    Chlorine  and  iodine  41  eliminate  hydrogen  and 
result  in  the  deposition  of  carbon,  in  accordance  with  the  following 
reactions  : 

C*Hy  +  Cl  =  CxHy^  +  HC1 

y  +  Cl  =  .C.-iHy-i  +  C  +  HC1 


Similar  reactions  take  place  with  iodine,  also  boron  fluoride.42 
The  relation  between  the  "iodine  number"  of  asphalts  and  their 
structure  has  also  been  investigated.43 

,  Halogens  seem  to  destroy  the  protective  colloids  that  keep  the 
colloidal  carbon  in  suspension  and  result  in  the  deposition  of  ele- 
mental carbon,  if  the  reaction  progresses  far  enough.  Upon  treat- 
ing asphalt  with  chlorine  gas  in  the  presence  of  a  trace  of  iodine  at 
200  to  250°  C.,  the  fusing-point  is  increased  materially,  and  a  hard, 
glossy  product  is  obtained  having  a  glossy  fracture.44  Similarly,  a 
soft  coal-tar  pitch  will  have  its  fusing-point  increased  from  25  or 
30°  F.  ,to  120°  F,,45  likewise  its  adhesiveness  increased.4*  It  i$ 
claimed  that  hexachlorethane  will  react  in  a  similar  manner.47  A 
process  has  also  been  proposed  which  involves  treatment  with 
chlorine  below  130°  C.  in  the  presence  of  antimony  chloride,  phos- 
phorus chloride,  or  iodine;  48  likewise  a  method  of  treating  with  con- 
centrated sulfuric  acid,  followed  by  FeCU,  AlCls,  or  PCls.49 


Ill  (/)  REACTIONS  WITH  METALLIC  SALTS  81 

(J)  REACTIONS  WITH  METALLIC  SALTS 

Bituminous  substances  act  as  "dispersoids,"  in  that  they  have 
the  property  of  dispersing  colloidal  solids,  including  certain  metal- 
lic salts.  Trinidad  asphalt  is  a  typical  example,  in  which  the  asphalt 
acts  as  a  dispersoid  for  adventitious  mineral  matter  of  colloidal 
nature,  consisting  principally  of  colloidal  clay.  That  the  clay  is 
present  in  a  colloidal  state  is  evidenced  by  the  following  facts :  ( i ) 
a  dilute  solution  of  Trinidad  asphalt  in  carbon  disulfide,  upon  stand- 
ing, retains  indefinitely  the  clay  in  suspension,  and  moreover  it 
cannot  be  separated  upon  centrifuging,  or  upon  passing  the  solution 
through  an  ultra-filter;  and  (2)  an  examination  of  the  solution 
through  the  ultra-microscope  shows  the  mineral  particles  to  be  in  a 
characteristic  state  of  active  motion,  known  as  Brownian  movement 
or  "pedesis,"  which  may  be  made  to  cease  under  the  influence  of  an 
electric  field  ("cataphoresis").  This  subject  will  be  discussed  fur- 
ther in  Chapter  XXIV  under  the  heading  "Colloidal  Particles — 
Liberated  'In  Situ'."  Other  metallic  salts  which  will  disperse  in 
bituminous  substances  include  sulfates  and  selenates,  chlorides,  ox- 
ides, acetates  and  borates. 


CHAPTER  IV 

GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND 
PYROBITUMENS 

GEOLOGY 

Age  of  the  Geological  Formations.  The  earth's  crust  has  been 
divided  into  natural  groups  or  strata  in  the  order  of  their  antiquity. 
There  are  five  main  divisions,  which  range  in  sequence  as  follows : 

1.  Quaternary  or  Post-tertiary,  representing  the  strata  now  in 
the  process  of  formation. 

2.  Tertiary  or  Caenozoic,  embracing  the  age  of  recent  life. 

3.  Secondary  or  Mesozoic,  representing  the  less  recent  life. 

4.  Primary  or  Paleozoic,  representing  the  so-called  "ancient 
life." 

5.  Archaean  or  Azoic,  representing  the  so-called  lifeless  strata. 

These  divisions  are  recognized  by  the  distinctive  organic  re- 
mains, fossils,  minerals  and  other  characteristics.  They  are  clas- 
sified into  various  "systems"  as  shown  in  Table  VI. 

The  systems  form  a  chronological  time-chart  indicating  the  rela- 
tive ages  of  the  earth's  strata.  The  systems  are  further  sub-divided 
into  groups  which  differ  in  different  localities,  but  it  will  be  unneces- 
sary to  consider  their  sub-classification  here. 

Petroleum  occurs  in  all  of  the  geological  horizons  from  the  Re- 
cent down  to  the  Pre-Cambrian.  Certain  systems  are  richer  than 
others,  especially  the  Pliocene,  Miocene,  Oligocene,  Eocene,  Car- 
boniferous, Upper  Devonian  and  Lower  Silurian  (Ordovician). 
Asphalts,  asphaltites  and  non-asphaltic  pyrobitumens  are  found  in 
all  the  systems  from  the  Pliocene  to  the  Silurian.  Mineral  waxes 
are  found  largely  in  the  Pliocene,  Miocene,  Oligocene,  Eocene  and 
Cretaceous. 

The  non-asphaltic  pyrobitumens  do  not  occur  in  the  older  Paleo- 
zoic formations  i.e.,  the  Silurian  or  Cambrian  Systems).  The 
Carboniferous  System  contains  the  most  valuable  coal  deposits;  the 
Permian  and  Triassic  Systems  contain  coals  of  inferior  quality,  and 

82 


IV 


CHARACTER  OF  THE  ASSOCIATED  MINERALS 


the  coals  found  in  the  Jurassic,  Cretaceous,  Eocene  and  Oligocene 
Series  are  still  more  inferior  in  quality.  Lignite  occurs  in  the  Oligo- 
cene and  Miocene  Series,  and  peat  in  the  Pliocene  and  Pleistocene. 
The  Pre-Cambrian  Series  consists  largely  of  crystalline,  metamor- 
phic  rocks  of  volcanic  and  igneous  origin.  The  non-asphaltic  pyro- 
bitumens,  as  might  be  expected,  do  not  occur  in  rocks  of  this  char- 
acter. Graphite,  however,  occurs  in  the  Pre-Cambrian  rocks,  and 
may  possibly  have  been  derived  from  vegetable  matter,  although  no 
signs  of  associated  plant  remains  have  been  found  in  these  rocks. 


ERA 

Quaternary  or  Post- 
tertiary  


Tertiary  or  Caenozoic. . 


Secondary  or  Mesozoic. 


TABLE  VI 

SYSTEM 

f  f  Historic  ^ 

I  Recent  or  Post-glacial  \  Prehistoric 
,.1  I  Neolithic 

[  Pleistocene  or  Glacial 

f  Pliocene 
I  Miocene 
' '  I  Oligocene 
I  Eocene 


Cretaceous  .  .  .  • 

r  Upper 
Middle 

Lower 

Jurassic  • 

Middle 

Lower 

Triassic 

Permian 

Carboniferous  < 

Swer 

Primary  or  Paleozoic. 


Devonian 


Silurian 


Cambrian. . 


f  Upper 
|  Middle 
[  Lower 

/Upper 

\  Lower  (Ordovician) 

f  Upper 
|  Middle 
[Lower 


Archaean  or  Azoic Pre-Cambrian 

The  particular  geological  system  is  of  value  in  enabling  us  to 
prospect  and  trace  deposits  of  bitumens  and  pyrobitumens  in  any 
given  locality. 

Character  of  the  Associated  Minerals.  Bitumens  and  pyrobitu- 
mens, with  but  few  exceptions,  are  found  in  sedimentary  deposits  of 
sand,  sandstone,  limestone  and  sometimes  in  shale  and  clay.  Rare 


84        GEOLOGY  AND  ORIGIN  Of  BITUMENS  AND  PYROBITUMENS        IV 

occurrences  have  been  reported  in  igneous  'rocks,  but  then  only  in 
very  small  quantities. 

Modes  of  Occur  .ence.  Bitumens  and  pyrobitumens  are  found  in 
nature  in  the  f oP :  wing  ways  : 

1.  Over  flews: 

(a)  Springs. 

(b)  Lakes. 

(c)  Seepages. 

2.  Impregnating  Rocks: 

(a)  Subterranean  pools  or  reservoirs. 

(b)  Horizontal  rock  strata. 

(c)  Vertical  rock  strata. 

3.  Filling  Veins: 

( a )  Caused  by  vertical  cleavage. 

[b )  Caused  by  upturning. 

c)  Caused  by  sliding. 

d)  Formed  by  sedimentation. 

Springs.  Petroleu;n  and  the  liquid  forms  of  asphalt  only  are 
found  in  springs  (Fig.  25).  These  emanate  from  a  fissure,  crevice, 
or  fault  which  permits  the  petroleum  or  liquid  asphalt  to  rise  to  the 
surface  from  some  depth.  Petroleum  or  asphalt  springs  have  been 
reported  in  various  parts  of  the  world,  but  are  rarely  of  commercial 
importance.  tl 

Lakes.  Asphalt  only  is  sometime^  found  in  lakes,  which  are  in 
reality  springs  on  a  very  large  scale  (Fig.  26).  Some  of  the  largest 
and  most  valuable  deposits  occur  in  this  form,  the  best  known  being 
the  lakes  at  Trinidad  and  Venezuela.  It  is  probable  that  the  as- 
phalt is  forced  up  from  below  in  a  liquid  or  semi-liquid  condition 
by  the  pressure  of  the  o\\  and  gas  underneath,  which  causes  it  to 
flow  through  a  fissure  ,or  fault  and  spread  over  a  large  area  at  the 
surface.  Lake  asphalts  are  moderately  soft  where  they  emanate, 
but  harden  on  exposure  to  the  elements. 

Seepage.  These  occur  in  the  case  of  petroleum  or  liquid 
asphalts,  and  usually  from  cliffs  or  mountains  bearing  impregnated 
rock.  Elmer  the  pressure  of  the  material  itself  or  the  heat  of  the 
sufi  causes  ^'certain  quantity,  Usually  not  very  large,  to  flow  out  of 
the  rock  and  rtin  towards  the  lower  level  (Fig.  27).  Seepages  are 
ofteft  found  where  d  ripidly  flowing  stream  of  water  cuts  its  way 


IV 


MODES  OF  OCCURRENCE 


85 


Spring 
FIG.  25 


FIG.  26 


91 


Miles 

Cap  Rock  (Shale) 
Oik  Oasj    0/'/\ 

\  "  -- 


Seepages 
FIG.  27 


Subteranean  J?ool  or  Reservoir 
FIG.  28 


Impregnated^Hprlzontat  Strata 
FIG.  29 


Impregnated,  Strata   in.  Thrust, 
FIG.  30 


Fault  Filling  caused  l?y  Cleavage 
FIG.  31 


Fault  Filling  caused  by  Upturning 
FIG.  32 


Vein  Filling  caused  by  Sliding  of  Strata          Veins  formect  by  Sedimentation 
FIG.  33  FIG.  34 


-JL.-1 


Pure        Rock     Alluvium    Sand        Sand     Limestone    Clay       Shale      Orartift 
Asphalt    Asphalt  Stone 

1  FIGS.  25-34, 


86       GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND  PYROBITUMENS         IV 

through  strata  of  rock  impregnated  with  petroleum  or  asphalt 
From  a  commercial  standpoint,  seepages  of  asphalt  or  petroleum 
are  of  little  value. 

Subterranean  Pools  or  Reservoirs.  Practically  all  deposits  of 
petroleum  of  any  magnitude  occur  below  the  surface  of  the  earth  in 
subterranean  "pools"  or  "reservoirs."  These  consist  of  porous 
sand,  sandstone,  limestone  (or  dolomite)  with  a  more  or  less  imper- 
vious rock  cover.  The  porous  bed  is  exemplified  by  coarse-grained 
sandstone,  conglomerate,  or  limestone.  The  limestone  may  have 
been  dense  as  it  existed  originally,  but  rendered  porous  in  the  course 
o£  time  by  conversion  into  dolomite,  with  the  consequent  production 
of  voids  due  to  shrinkage,  since  dolomite  occupies  less  space  than 
the  original  limestone.  The  petroleum  is  carried  in  the  interstices 
of  the  porous  rock  and  prevented  from  volatilizing  or  escaping  by 
an  impervious  cover  known  as  the  "cap-rock,"  usually  composed  of 
shale  or  a  dense  limestone.  The  main  supplies  of  petroleum  have 
been  obtained  from  regions  which  have  been  comparatively  undis- 
turbed by  terrestrial  movements.  In  such  cases  the  accumulation 
of  petroleum  underneath  forms  what  is  known  as  a  "pool"  or  "res- 
ervoir" (Fig.  28).  * 

Impregnated  Rock  in  Strata.  Liquid  to  semi-liquid  asphalts 
occur  in  this  manner.  Rocks  impregnated  with  asphalt  are  pro- 
duced in  two  ways,  viz.  : 

1 i )  By  the  gradual  evaporation  and  hardening  of  an  asphaltic 
petroleum  due  perhaps  to  the  disturbing  or  removal  of  the  cap-rock, 
leaving  the  asphalt  residue  filling  the  interstices  of  the  stratum  car- 
rying it.    These  are  usually  found  in  horizontal  strata  (Fig.  29). 

(2)  By  the  liquid  asphalt  being  forced  upward  under  pressure, 
or  drawn  upward  by  capillarity  from  underlying  strata  into  a  porous 
rock  layer  above  it.     These  are  usually  found  in  the  region  of  a 
"thrust"  or  upturning  of  the  earth's  strata  (Fig.  30). 

Filling  Feins.  The  harder  asphalts,  asphaltites  and  asphaltic 
pyrobitumens  are  most  commonly  found  filling  fissures  in  a  more  or 
less  vertical  direction,  caused  by  "faulting."  In  geology,  a  "fault" 
is  a  more  or  less  vertical  crack  in  the  earth's  surface  brought  about 
by  the  contraction  and  uneven  settling  of  the  strata.  This  is  occa- 
sioned by  a  greater  movement  in  the  rock  on  one  side  of  the  fault's 
plane  than  on  the  other,  as  illustrated  in  Fig.  31,  or  by  the  upturning 


IV  MOVEMENT  OF  BITUMENS  IN  THE  EARTH'S  STRATA  87 

of  a  section  of  the  earth's  crust  as  shown  in  Fig.  32.  Faults  allow 
the  liquid  or  molten  asphalt  to  force  its  way  up  from  underneath 
and  fill  the  crevice.  As  will  be  described  later,  after  the  asphalt 
hardens  in  the  fault,  it  might  in  time  become  metamorphosized  and 
converted  into  an  asphaltite  or  asphaltic  pyrobitumen.  Non-asphal- 
tic  pyrobitumens  are  never  found  in  faults,  probably  because  they 
are  incapable  of  softening  or  melting  under  the  action  of  heat,  either 
in  their  original  state  or  afterwards. 

Sometimes  we  find  the  harder  asphalts,  asphaltites  and  asphaltic 
pyrobitumens  filling  a  more  or  less  horizontal  fissure  or  cleavage 
crack,  brought  about  by  the  sliding  of  two  strata,  one  upon  the 
other.  The  opening  between  the  strata  becomes  filled  with  the  liquid 
or  melted  asphalt,  forced  up  under  pressure  through  a  crevice  from 
below,  which  then  hardens,  giving  rise  to  a  horizontal  vein  as  shown 
in  Fig.  33. 

Horizontal  veins  are  sometimes  derived  from  prehistoric  asphalt 
"lakes,"  perhaps  similar  to  our  present  Trinidad  or  Venezuela  lakes. 
In  time,  these  harden,  and  become  submerged  in  water,  due  perhaps 
to  a  movement  in  the  level  of  the  earth's  crust.  The  water  permits 
the  sedimentation  of  mineral  matter,  so  that 'the  lake  is  gradually 
converted  into  a  horizontal  vein.  If  the  liquid  asphalt  again  breaks 
through  a  fault  or  fissure,  it  will  form  a  superimposed  vein,  or  per- 
haps a  series  of  such  veins  between  sediments,  as  shown  in  Fig.  34. 

In  the  case  of  non-asphaltic  pyrobitumens,  the  veins  were  un- 
questionably formed  by  a  process  of  sedimentation.  The  vegetation 
from  which  these  were  derived,  originally  grew  in  swampy  or  marshy 
localities,  presumably  about  the  mouths  of  rivers.  As  the  vegetation 
died,  it  became  covered  with  sediments  of  sand  or  clay  carried  down 
by  the  water,  or  by  calcium  carbonate  precipitated  from  the  water, 
which  in  turn  formed  soil  for  subsequent  growths.  These  gave  rise 
to  the  future  veins  of  non-asphaltic  pyrobitumens,  which  are  similar 
structurally  to  the  preceding  (Fig.  34). 

Movement  of  Bitumens  in  the  Earth's  Strata.  It  is  a  singular 
fact  that  petroleum,  mineral  waxes,  asphalts  and  asphaltites  are  not 
always  found  in  the  same  locality  in  which  they  originated.  They 
have  the  power  of  migrating  from  place  to  place,  and  many  deposits 
are  still  in  the  process  of  migration.  A  "primary  deposit"  is  one  in 
which  the  bituminous  material  is  still  associated  with  the  same  rocks 


88        GEOLOGY  ANf>  ORIGIN  OF  BITUMENS  AND  PYROSITUMENS        IV 

in  which  it  originated,  A  "secondary  deposit''  is  one  to  which  the 
material  has  subsequently  migrated.  Bitumens  usually  migrate 
while  in  a  liquid  or  melted  condition,  although  in  certain  rare  in- 
stances the  migration  has  been  induced  by  the  action  of  flowing 
water  while  the  bitumen  is  in  the  solid  state. 

The  main  causes  for  the  movement  of  native  bituminous  sub- 
stances in  the  earth's  surface  are  as  follows: 

1 I )  Hydrostatic  Pressure,     This  is  largely  responsible  for  the 
accumulation  of  petroleum  in  pbols  or  reservoirs.    At  some  distance 
below  the  earth's  surface  there  is  an  accumulation  of  ground  water, 
the  level  of  which  wries  in  different  localities  and  during  different 
seasons.    The  petroleum,  being  lighter  than  the  water,  floats  on  its 
surface.    As  the  level  of  the  ground  water  varies,  it  will  move  the 
petroleum  about  through  interstices  in  the  rock.    The  water  tends  to 
push  the  oil  ahead  of  it,  and  this  will  account  for  the  accumulation 
of  the  petroleum  in  the  form  of  pools  or  reservoirs  underneath  a 
cap  of  a  dense  and  non-porous  strata  through  which  it  cannot  per- 
meate.   This  will  also  explain  why  there  is  often  an  accumulation 
of  petroleum  in  the  ground  near  the  top  of  a  hill  or  mountain.    Oil 
and  gas  are  often  encountered  under  pressure,  due  to  the  hydro- 
static head  of  water. 

Hydrostatic  pressure  may  also  cause  the  migration  of  solid  as- 
phalts, as  for  example  in  the  case  of  the  Dead  Sea,  where  masses 
become  detached  from  the  bottom  and  are  caused  to  float  upward 
by  the  higher  gravity  of  the  water,  due  to  the  large  percentage  of 
salt  dissolved  in  it. 

(2 )  Gas  Pressure.     It  is  probable  that  the  action  of  the  heat  or 
other  forces  below  the  surface  of  the  earth,  tend  partially  to  va- 
porize certain  bitumens,  so  that  the  resulting  gas  will  force  them 
into  the  overlying  strata  near  the  surface.     In  other  instances  the 
effect  of  faulting,  crumpling,  upturning,  erosion  and  other  move- 
ments of  the  earth's  strata  exposes  the  oil-  or  asphalt-bearing  forma- 
tions, and  enables  the  gas  pressure  to  force  them  to  the  surface. 
Natural  gas  exists  under  great  pressure  in  certain  localities.    Many 
gas  wells  in  the  Baku  and  Pennsylvania  fields  have  registered  a  pres- 
sure of  600  to  800  lb.,  and  even  as  high  as  1000  Ib.  per  square  inch. 
This  may  be  accounted  for  by  the  fact  that  as  the  gas  is  constantly 
being  generated,  it  accumulates  inside  of  the  earth's  surface  and 
has  no  access  to  escape  owing  to  the  density  of  the  strata  above. 

(3)  Capillary.     This  force  takes  place  m  dry  porous  rocks 
and  acts  on  permanently  liquid  bitumens,  of  bitumens  solid  at  ordi- 
nary temperatures  but  transformed  to  the  melted  state  by  the  action 
of  heat.    Under  these  conditions  the  bitumen  will' soak  into  the 


IV  ORIGIN  AND  METAMORPHOSIS  OF  BITUMENS,  ETC,  89 

pores  of  the  rock  or  sand  and  gradually  fill  the  interstices.  Capil- 
larity is  a  very  much  stronger  force  than  gravity,  although  other 
forces,  such  as  the  action  of  heat  (see  under  5)  may  be  partly  re- 
sponsible. The  finer  the  pores  in  the  rock,  the  greater  will  be  the 
capillary  force.  Rocks  saturated  with  moisture  tend  to  resist  the 
action  of  capillarity,  wrhich  is  most  effective  in  the  dry  state. 

(4)  Gravitation.     The  natural  weight  of  the  overlying  strata 
caused  by  gravitation  sets  up  a  pressure  where  there  are  accumula- 
tions pf  petroleum  or  other  forms  of  liquid  bitumen  underneath^ 
and  if  a  fissure  or  fault  occurs  in  the  earth's  crust,  the  bitumen, 
being  softer  than  the  surrounding  rock,  will  be  forced  to  the  sur- 
face.   Gravitation  is  therefore  selective  in  its  action  and  by  exerting 
a  greater  pull  on  the  heavier  bodies  will  tend  to  force  the  lighter 
ones  upward.     Under  other  circumstances,  where  the  substances 
are  not  confined,  the  result  of  gravitation  is^  to  cause  the  petroleum 
or  liquid  asphalt  to  ooze  from  the  overlying  rock  matrix  in  the 
form  of  "seepages." 

(5 )  Effect  of  Heat.     Heat  is  also  a  large  factor  in  causing  the 
migration  of  bituminous  substances.     Its  effect  is  variable.     Undter 
certain  circumstances  it  will  convert  the  solid  bitumens  into  a  liquid 
state  and  thus  enable  them  to  be  acted  upon  by  the  various  forces 
considered  previously.    Under  other  conditions,  heat  in  the  interior 
of  the  earth  will  vaporize  the  bitumens  such  as  petroleum  and  force 
them  upward.    Again,  if  the  heat  is  sufficiently  intense,  it  is  apt  to 
cause  the  bitumens  to  undergo  destructive  distillation,  the  distillate 
condensing  in  the  upper  and  cooler  layers. 

ORIGIN  AND  METAMORPHOSIS  OF  BITUMENS  AND  ASPHALTIC 

PYROBITUMENS 

Probable  Origin  of  Bitumens  and  Asphaltic  Pyrobitumens.  Al- 
though much  has  been  written  on  this  subject,  no  generally  accept- 
able conclusions  have  been  reached.  The  discussion  has  in  the  main 
centered  about  the  origin  of  petroleum,  as  this  is  conceded  to  be  the 
mother  substance,  from  which  the  other  bitumens  and  pyrobitumens 
are  supposed  to  have  been  produced  by  a*  process  of  metamorphosis. 
The  theories  have  been  divided  into  two  classes,  namely,  the  inor- 
ganic and  the  organic.  We  will  consider  these  in  greater  detail. 

Inorganic  Theories.  It  is  contended  that  the  interior  of  the 
earth  contains  free  alkaline  metals,  presumably  in  a  melted  condi- 
tion. These  at  high  temperatures  would  react  with  carbon  dioxide, 
forming  acetylides  which  in  turn  produce  hydrocarbons  of  the  acety- 
lene series  upon  coming  in  contact  with  water*  The  acetylenes  being 


90       GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND  PYROBITUMENS        IV 

unsaturated  would  have  a  tendency  to  combine  with  free  hydrogen 
and  give  rise  to  the  olefine  and  paraffin  series. 

Still  another  theory  based  on  similar  lines  assumes  the  presence 
of  metal  carbides,  including  iron  carbide,  some  distance  below  the 
surface  of  the  earth.  These  are  supposed  to  decompose  on  coming 
in  contact  with  water  and  produce  hydrocarbons,  which  upon  con- 
densing in  the  cooler  upper  strata  give  rise  to  petroleum.  This, 
however,  is  mere  speculation,  for  no  iron  carbide  has  ever  been 
found.  The  occurrence  of  hydrocarbon  gases  in  volcanic  emana- 
tions has  been  cited  to  substantiate  this  theory. 

The  cosmical  hypothesis  is  based  upon  the  assumption  that  hy- 
drocarbons were  present  in  the  atmosphere  which  originally  sur- 
rounded the  earth,  after  it  had  been  thrown  off  by  the  sun.  These 
hydrocarbons  are  claimed  to  have  been  formed  by  a  direct  combina- 
tion of  the  elements  carbon  and  hydrogen  in  the  cosmic  mass.  As 
the  earth  cooled,  the  hydrocarbons  condensed  in  the  earth's  crust, 
giving  rise  to  deposits  similar  to  those  existing  to-day.  This  theory 
has  also  been  connected  with  the  carbide  theories,  upon  the  assump- 
tion that  at  the  high  temperatures  to  which  the  gases  must  have 
been  subjected  at  the  time  they  were  thrown  off  by  the  sun,  and 
before  they  condensed,  the  first  compounds  formed  were  carbides, 
silicides,  nitrides,  and  the  like.  As  oxidation  would  not  commence 
until  some  time  later,  it  is  assumed  that  these  carbides  would  remain 
locked  up  in  the  interior  of  the  earth  for  geologic  ages,  and  then 
gradually  give  rise  to  hydrocarbons  upon  being  decomposed  through 
the  agency  of  water. 

Vegetable  Theories.  It  has  long  been  known  that  certain  hydro- 
carbons result  during  the  decay  of  vegetation.  The  hydrocarbon 
methane  (CH4),  otherwise  known  as  "marsh  gas"  is  produced  in 
this  manner,  but  only  in  comparatively  small  amounts.  Similarly, 
methane  has  been  detected  in  the  gases  resulting  during  the  decay 
of  seaweed. 

It  has  been  shown  by  others  that  under  certain  conditions  hydro- 
carbons may  be  produced  artificially  by  the  fermentation  and  decay 
of  certain  forms,  of  cellulose,  including  woody  fiber.  Still  other 
scientists  maintain  that  petroleum  is  produced  by  microscopic  plants 
known  as  diatoms,  which  occur  abundantly  in  peat  beds,  and  certain 
bogs.  These  organisms  are  found  to  contain  minute  globules  of 


IV  ORIGIN  AND  METAMORPHOSIS  OF  BITUMENS,  ETC.  91 

oily  matter  distributed  in  the  plasma,  and  moreover,  a  waxy  sub- 
stance resembling  ozokerite  may  be  extracted  by  solvents  from  the 
diatomaceous  peat.  It  is  contended  that  this  oil  will  in  time  and 
under  pressure  become  converted  into  liquid  petroleum,  and  at 
higher  temperatures  and  pressures  possibly  into  asphalt.  In  sup- 
port of  this  hypothesis  a  bed  of  peat  has  been  described  near  Stettin, 
Germany,  consisting  largely  of  diatoms  and  from  which  hydro- 
carbons have  been  extracted  in  quantities  up  to  4  per  cent. 

Another  theory  based  on  similar  lines  infers  that  petroleum  is 
derived  from  a  slimy  substance  rich  in  organic  matter  known  as 
"sapropel,"  composed  largely  of  algae,  which  accumulates  at  the 
bottom  of  stagnant  waters.  This  slime  becomes  covered  with  sedi- 
ments which  through  the  agency  of  moisture,  time  and  pressure,  is 
assumed  to  give  rise  to  petroleum,  and  under  certain  conditions,  to 
asphalt  It  is  of  interest  to  note  that  petroleum  and  asphalt  have 
been  produced  in  the  laboratory  by  the  hydrolysis  of  algae  in  acid 
solutions.1 

In  a  similar  manner,  bitumens  are  claimed  to  have  been  formed 
from  deposits  of  vegetable  matter,  including  various  marine  plants, 
seaweeds,  etc.,  which  accumulate  at  the  bottom  of  the  ocean.  Just 
as  the  non-asphaltic  pyrobitumens  (e.g.,  coal)  are  produced  by  the 
decomposition  of  terrestrial  vegetation,  it  is  contended  that  bitumens 
have  arisen  from  the  decay  of  marine  plants.  This  theory  has  a 
number  of  adherents.  The  optical  activity  of  certain  petroleums  h^s 
been  cited  to  substantiate  the  contention,  since  oils  derived  from 
organic  matter  can  only  possess  this  property.  It  has  been  proven 
that  hydrocarbons  produced  from  inorganic  substances,  such  as 
metal  carbides,  do  not  exhibit  optical  activity. 

Still  another  theory,  advocating  the  vegetable  origin  of  petro- 
leum, assumes  its  derivation  from  peat,  lignite  or  coal,  which  have 
been  subjected  to  a  sufficiently  high  temperature  to  undergo  a  prqc- 
ess  of  destructive  distillation,  resulting  in  the  production  of  liquid 
and  gaseous  hydrocarbons.  This  is  supposed  to  have  occurred  at 
great  depths  below  the  earth's  surface  and  the  hydrocarbons  con- 
densed in  upper  layers. 

The  asphaltic  pyrobituminous  shales  are  similarly  claimed  to 
have  generated  petroleum  under  the  action  of  heat,  based  on  the 
well-known  fact  that  when  these  shales  are  distilled  commercially, 


92        GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND  PYROBITVMENS        W 

petroleum-like  oils  are  produced.  It  is  contended  that  the  shales 
themselves  were  derived  from  gelatinous  algae  whose  remains  are 
still  recognizable  in  certain  of  them  with  the  aid  of  a  microscope. 

Animal  Theories.  In  a  similar  manner,  petroleum  and  asphalt 
are  supposed  to  have  been  produced  from  the  accumulation  of  ani- 
mal matter  at  the  bottom  of  the  ocean,  which  in  time  decomposed 
into  hydrocarbons.  The  presence  of  nitrogen  in  all  forms  of  bitu- 
men is  cited  in  substantiation  of  its  production  from  albuminoid 
matter.  The  remains  of  molluscs  and  fish  are  present  in  certain 
asphaltic  pyrobituminous  shales,  including  the  Albert  series  of  New 
Brunswick,  and  in  many  rocks  carrying  petroleum  and  asphalt. 
Deposits  of  the  latter  have  been  reported  in  Galicia,  Wyoming,  and 
are  particularly  noticeable  in  the  case  of  oil  and  asphalt  deposits  in 
Uvalde  County,  Texas,  and  southeastern  California.  In  Egypt, 
shells  are  also  found  filled  with  bitumen.  Others  contend  that  the 
living  cells  are  in  some  manner  absorbed  into  the  pores  of  coral 
reefs,  and  that  these  in  time  result  in  the  formation  of  bituminous 
limestone. 

Substances  closely  resembling  petroleum  or  bitumens  have  been 
produced  artificially  by  subjecting  fish  albumin  to  heat,  under  pres- 
sure. Asphalt-like  substances  have  been  produced  by  heating  gela- 
tine, casein,  calcium  carbonate  and  magnesium  carbonate  in  an  at- 
mosphere of  hydrogen  at  240°  C  under  pressure  of  33  atm.  The 
solution  of  the  resultant  product  in  carbon  disuifide  exhibited 
Brownian  movement  and  the  particles  were  flocculated  by  ether.2 
Animal  fats  have  similarly  been  converted  into  hydrocarbons  boil- 
ing below  300°  C.  The  conversion  of  fats  and  albuminous  sub- 
stances into  petroleum  is  said  to  depend  upon  three  factors,  namely, 
pressure,  temperature  and  time.  The  variations  in  the  composition 
of  petroleum  found  in  different  localities,  are  accounted  for  by  varia- 
tions in  one  or  more  of  these  factors. 

In  conclusion  it  might  be  stated  that  probably  all  three  theories 
embody  certain  elements  of  truth.  The  cosmical  hypothesis  is  sus- 
tained by  the  fact  that  hydrocarbons  have  often  been  found  in  me- 
teorites, although  this  supposition  has  been  refuted.3  The  inorganic 
theory/isf  boi-ne  out  by  the  fact  that  hydrocarbons  occur  in  volcanic 
emanations.:  The  vegetable  and  animal  theories  in  turn  are  sup- 
ported by  the  presence  of  bitumens  and  pyrobitumens  in  rocks  of 


IV  METAMORPHOSIS  OF  MINERAL  WAXES,  ETC.  93 

sedirheritary  character,  often  carrying  vegetable  and  animal  fossil 
remains.  Mabery  contends  that  the  presence  of  nitrogen  in  petro- 
leum derived  from  all  the  principal  oil  fields,  exists  in  the  form  of 
tombinations  which  could  only  have  had  their  origin  in  vegetable 
or  animal  remains.4 

It  is  highly  probable,  therefore,  that  bitumens  owe  their  origin 
to  two  or  more  of  the  theories  which  have  been  discussed,  and  which 
would  account  for  their  varying  chemical  composition  and  physical 
characteristics. 

Metamorphosis  of  Mineral  Waxes,  Asphalts,  Asphaltites  and 
Asphaltic-Pyrobitumens  from  Petroleum.  Although  there  seems 
to  be  a  wide  difference  of  opinion  regarding  the  origin  of  petroleum 
authorities  are  pretty  well  agreed  that  petroleum  when  once  formed, 
is  gradually  converted  into  the  other  types  of  bitumen  and  pyro- 
bitumens,  under  the  influence  of  time,  heat  and  pressure.  This 
process  of  transformation  is  known  as  "metamorphosis." 

Several  chemical  processes  are  involved,  e.g.,  oxidation,  sulfuri- 
zation,  polymerization  (i.e.,  the  combination  of  like  molecules)  and 
condensation  (i.e.,  the  combination  of  unlike  molecules).  Some 
natural  asphalts  are  derived  through  the  slow  evaporation  of  lower 
boiling-point  fractions  from  the  original  petroleum;  others  indicate 
conversion  by  heat  and  pressure;  still  others  show  evidence  of  slow 
oxidation.  It  is  likely  that  a  combination  of  these  three  processes 
occur  simultaneously.  Asphalt  associated  with  tar  sands  has  under- 
gone little  change  other  than  the  loss  of  volatile  fractions;  on  the 
other  hand,  gilsonite,  glance  pitch  and  grahamite  appear  to  be  prod- 
ucts of  reaction  and  conversion,  rather  than  products  of  evaporation. 

It  is  contended  that  mineral  matter  in  a  finely  divided  form,  as 
for  example  "colloidal"  clay,  hastens  the  transformation  of  natural 
gas  or  petroleum,  by  acting  as  a  catalyzer.  This  theory  is  advanced 
by  Clifford  Richardson.5  In  studying  the  well-known  Trinidad 
asphalt  lake,  Richardson  concludes  that  an  asphaltic  petroleum 
existing  at  a  considerable  depth  is  converted  into  a  more  solid  form 
of  bitumen,  namely  asphalt,  upon  being  thoroughly  emulsified  with 
colloidal  clay,  sand  and  water  through  the  medium  of  natural  gas 
at  a  high  pressure.  During  the  metamorphosis,  hydrogen  is  gradu- 
ally eliminated,  the  hydrocarbons  becoming  enriched  in  carbon,  and 
from  a  chemical  standpoint  more  complex  structurally.  The  changes 


94        GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND  PYROBITUMENS        IV 

brought  about  during  this  process  may  be  regarded  as  a  form  of 
polymerization,  in  which  the  hydrocarbon  molecules  become  rear- 
ranged into  more  complex  molecules  of  higher  molecular  weight 

The  simplest  hydrocarbons  are  present  in  petroleum.  Those  in 
mineral  waxes  are  somewhat  more  complex,  and  both  the  structural 
complexity  and  the  molecular  weight  increase  in  the  case  of  asphalts 
and  the  asphaltic  pyrobitumens.  There  are  no  sharp  lines  of  de- 
marcation between  the  various  types  of  bitumens  or  asphaltic  pyro- 
bitumens. Each  class  gradually  merges  into  another,  and  specimens 
will  often  be  found  on  the  border  line,  so  that  it  is  difficult  to  decide 
to  which  class  they  actually  belong. 

From  this  viewpoint  we  may  regard  petroleums  as  passing  in 
gradual  stages,  uftder  the  influence  of  time,  heat,  pressure  and  cata- 
lyzers into  the  soft  native  asphalts,  which  in  turn  pass  into  harder 
native  asphalts,  and  then  into  asphaltites  and  finally  into  the  asphal- 
tic pyrobitumens  and  asphaltic  pyrobituminous  shales.6 

TABLE  VII 

PETROLEUM  (Crude  Oil) 


/  \ 

Non-asphaltic  Petroleum  Semi' Asphaltic  and  Asphaltic  Petroleums 

I  I 

Mineral  "Waxes  Native  Asphalts 

(  Ozokerite  )  / *• \ 

Pure  and  Impure 

Fairly  Pure  Asphalts  (Rock  Asphalts) 

J  I 

Asphaltites  (Impure  Asphaltites) 

I  I 

Asphaltic  Pyrobitumens  Asphaltic  Pyrobituminous  Shales 

CELLULOSE  (Woody  Fiber) 


Vegetable  Growths  (Sphagnum)  in  Bogs,  Swamps,  etc.      Trees,  etc* 

Jr 

Peat 
Impure  (Associated  with  Mineral  Matter)  Pure 

Lignite  Shales  Lignite 

I  I 

Coal  Shales  Bituminous  Coal 

Anthracite  Coal 
Graphite 


IV  ORIGIN  OF  NON-ASPHALTIC  PYROBITUMENS  95 

It  is  highly  probable  that  all  deposits  of  asphalt  are  produced 
by  metamorphosis  from  asphaltic  petroleum.  Similarly  it  seems 
likely  that  all  deposits  of  mineral  wax,  such  as  ozokerite,  etc.,  result 
from  the  metamorphosis  of  paraffinaceous  petroleum. 

Elaterite,  wurtzilite,  albertite,  impsonite  and  the  asphaltic  pyro- 
bituminous  shales  represent  the  final  stages  in  the  metamorphosis 
of  petroleum.  The  first  four  are  comparatively  free  from  mineral 
matter.  If  the  latter  predominates,  the  product  is  known  as  an 
asphaltic  pyrobituminous  shale.  The  non-mineral  matter  contained 
in  these  shales  has  the  same  general  characteristics  as  elaterite, 
wurtzilite,  albertite  or  impsonite,  depending  upon  how  far  the  meta- 
morphosis has  progressed. 

Table  VII  gives  an  approximate  idea  of  the  natural  metamor- 
phosis of  bitumens  and  pyrobitumens,  one  from  another.7 

ORIGIN  AND  METAMORPHOSIS  OF  NON-ASPHALTIC 
PYROBITUMENS 

The  origin  of  non-asphaltic  pyrobitumens  has  been  definitely 
established.  The  associated  fossil  remains  clearly  prove  that  these 
have  been  derived  from  vegetable  matter  containing  cellulose,  a 
carbohydrate  having  the  empirical  formula  (CeHioOs)^ 

The  decomposition  of  cellulose  when  the  air  is  partly  or  wholly 
excluded,  as  would  be  the  case  when  buried  in  the  ground,  results  in 
the  loss  of  carbon  dioxide,  methane,  and  water.  In  this  manner, 
cellulose  ultimately  yields  a  series  of  products  grouped  under  the 
heading  of  non-asphaltic  pyrobitumens.  The  conditions  favorable 
to  their  production  seem  to  be  the  growth  of  vegetable  substances 
about  the  mouths  of  rivers,  combined  with  a  change  in  water-level. 
The  sediment  carried  down  by  the  river,  formed  beds  of  sand  or 
clay  which  sealed  the  vegetation  in  between  the  strata.  In  this  man- 
ner the  vegetable  matter  was  protected  from  atmospheric  oxidation 
and  at  the  same  time  probably  subjected  to  fermentative  heat,  also 
to  a  gradually  increasing  pressure,  as  successive  layers  accumulated. 
The  vegetation  doubtlessly  embraced  many  different  kinds,  including 
trees,  ferns,  grasses,  mosses,  and  the  like.  Fossil  ferns  are  still 
clearly  evident  in  coal  beds.  In  other  cases  carbonized  trees,  roots 
and  fibrous  tissue  are  recognizable,  and  in  still  others,  the  resins 
originally  present  in  the  wood  are  found  intact.  Amber  and  fossil 


36        GEOLOGY  AND  ORIGIN  OF  BITUMENS  AND  PYROBITUMENS        IV 

copal  often  occur  in  peat,  and  large  masses  of  vegetable  resin  have 
been  identified  in  beds  of  lignite  and  bituminous  coal 

Peat  represents  the  first  stage  in  the  metamorphosis  of  coal  from 
vegetable  matter,  and  occurs  in  bogs  or  other  swampy  places.  Very 
often  on  the  surface  of  a  bog  or  swamp  we  see  the  still  living  and 
growing  plants.  A  little  below,  we  find  their  decayed  remains,  and 
still  deeper,  a  black  glutinous  substance  saturated  with  moisture, 
known  as  "peat"  8 

The  exact  nature  of  the  changes  which  take  place  in  the  trans- 
formation of  vegetable  matter  into  peat  is  not  clearly  understood. 
The  ultimate  analysis  shows  that  the  percentages  of  hydrogen  and 
oxygen  have  diminished,  and  carbon  correspondingly  increased.  In 
the  most  recent  deposits,  peat  is  loosely  compacted,  but  as  it  accumu- 
lates under  the  sediments,  it  becomes  compressed.  A  bed  which 
was  possibly  once  a  foot  thick  might  shrink  to  several  inches.  In 
all  probability  the  pressure  developed  by  the  superimposed  layers, 
aids  in  the  transformation  of  peat  into  coal. 

Lignite  9  or  browncoal  is  intermediate  between  peat  and  bitumi- 
nous coal.  The  most  recent  deposits  approach  peat  in  composition, 
and  the  oldest  merge  into  bituminous  coal.  Lignite  contains  a  larger 
percentage  of  carbon  and  smaller  percentages  of  hydrogen  and  oxy- 
gen than  peat  It  is  often  associated  with  mineral  resins  or  wax-like 
hydrocarbons  *  which  may  be  extracted  by  means  of  solvents, 

Jet,  gagate,  azabache  and  "black  amber"  are  species  of  lignite. 

Cannel  coal 10  and  bog-head  coal  and  torbanite  are  in  reality  a 
sub-class  of  bituminous  coal,  rich  in  volatile  matter.  The  former 
are  supposed  to  have  been  derived  from  spores,  spore  cases,  and 
resinous  or  waxy  products  of  plants  (e.g.,  sapropel).  The  absence 
of  woody  material  gives  cannel  coal  a  uniform  texture  and  grain 
not  present  in  other  coajs,  so  that  it  breaks  with  a  conchoidal  frac- 
ture, and  a  splinter  ignites  in  contact  with  a  lighted  match,  burning 
like  a  candle,  whence  it  derives  its  name. 

*The  associated  resins  or  waxes,  or  asphalts,  as  they  are  termed  by  some,  have  been 
described  under  various  names,  including:  Anthracoxenite,  Bombiccite,  Branchite,  Bu- 
tyrellite,  Dinite,  Dopplerite,  Duxite,  Dysodile,  Euosmite,  Fichtelite,  Geomyficite,  Hartine, 
Hartite,  Hofmannite,  lonite,  Koflachite,  Leucopetrin,  Leucopetrite,  Melanchyme,  Mellite, 
Middletonite,  Muckite,  Neudorfite,  Neft-Gil,  Phytocollite,  Pianzke,  Pyronetin,  Refikite, 
Retinasphaltum,  Retinite,  Rochlederite,  Schleretinite,  Sieburgite,  Trinkerite,  \Valchowite, 
Wheelerite,  etc.  ;  -  , 


IV  ORIGIN  OF  NON-ASPHALTIC  PYROBITUMENS  97 

Bituminous  coal  falls  between  lignite  and  anthracite  coal.  It  is 
often  a  matter  of  difficulty  to  determine  where  the  lignites  stop  and 
the  bituminous  coals  begin;  similarly,  the  line  of  demarcation  be- 
tween bituminous  and  anthracite  coals  is  not  very  distinct.  Bitu- 
minous coals  contain  a  larger  percentage  of  carbon  and  smaller 
percentages  of  hydrogen  and  oxygen  than  lignite.  The  name  "bi- 
tuminous coal"  is  derived  from  the  fact  that  this  coal  apparently 
softens  and  undergoes  fusion  at  a  temperature  somewhat  below  that 
of  actual  combustion.  The  term,  however,  is  a  misnomer.  The 
softening  which  takes  place  marks  the  point  at  which  destructive 
distillation  commences,  accompanied  by  the  formation  of  gaseous 
hydrocarbons.  "Bitumen"  does  not  actually  exist  in  bituminous 
coal.  That  portion  which  dissolves  in  solvents  (e.g.,  xylol,  phenol, 
tetralin,  etc.)  has  been  termed  "bituminic  substance,"  since  it  re- 
sembles bitumens.  The  insoluble  portion  has  been  termed  the  "lig- 
nitic  residue,"  since  it  resembles  lignite.  Bituminous  coals  contain 
a  substantial  portion  of  volatile  matter,  which  causes  them  to  burn 
more  rapidly  than  anthracite,  and  with  a  larger  amount  of  flame. 
The  so-called  "coking  coal"  is  a  class  of  bituminous  coal,  used  in 
the  manufacture  of  coke.  The  relationship  between  bitumens  and 
coal  has  also  been  traced  by  the  similarity  of  the  substances  sepa- 
rated by  the  selective  action  of  certain  solvents,  in  their  deportment 
under  heat,  vacuum  distillation,  behavior  towards  chemical  agents, 
etc.11 

Anthracite  coal  represents  the  final  stage  in  the  transformation 
of  vegetable  matter  into  a  non-crystalline  form.  It  contains  definite 
proportions  of  hydrogen  and  oxygen.  Certain  forms  of  anthracite 
approach  graphite  in  their  composition.  Graphite  on  the  other  hand 
is  a  crystallized  mineral  composed  entirely  of  carbon,  and  which  is 
supposed  to  represent  the  final  stage  in  the  metamorphosis  of  coal. 
The  mode  of  occurrence  and  microscopic  structure  of  graphite  de- 
posits corresponds  closely  with  those  of  coal,  giving  rise  to  the  belief 
that  both  were  derived  from  a  common  source. 


CHAPTER  V 

ANNUAL    PRODUCTION    OF    BITUMINOUS    SUBSTANCES 
AND   THEIR   MANUFACTURED   PRODUCTS 

PRODUCTION  OF  ASPHALTS,  ASPHALTITES  AND  ASPHALTIC 

PYROBITUMENS 

World  Production.  Deposits  of  natural  asphalts  have  been  dis- 
covered in  all  parts  of  the  world.  Table  VIII,  compiled  from  data 
furnished  by  the  Department  of  Interior  of  the  U.  S.  Geological 
Survey,  shows  the  total  production  of  all  forms  of  native  asphalts 
(including  pure  and  rock  asphalts),  asphaltites  and  asphaltic  pyro- 
bitumens,  from  1906  to  1931  inclusive,  as  far  as  reliable  statistics 
are  available.1 

In  1931,  the  United  States  produced  the  largest  quantity  of 
native  asphalts,  having  assumed  the  lead  since  1920.  Italy  ranks 
second,  followed  by  Trinidad,  Germany,  France  and  Venezuela,  in 
the  sequence  stated. 

Production  in  the  United  States.  Table  IX  gives  the  total 
production  by  states  in  the  United  States  of  natural  asphalts,  as- 
phaltites and  asphaltic  pyrobitumens  for  the  years  1911  to  1935 
inclusive,  and  Table  X  gives  the  production  by  varieties  of  natural 
asphalts,  asphaltites,  asphaltic  pyrobitumens  and  petroleum  asphalts 
from  1900  to  1935  inclusive. 

No  appreciable  tonnage  of  asphalt  was  produced  in  the  United 
States  until  1883,  when  about  35,000  tons  was  imported  mainly  from 
Trinidad,  which  found  its  way  into  pavements.  Prior  to  this,  rela- 
tively small  quantities  of  Trinidad  was  used,  whereas  European 
rock  asphalts  were  imported  for  this  purpose.  In  1892  Trinidad 
asphalt  had  displaced  most  of  the  European  products,  and  in  that 
same  year  Bermudez  asphalt  made  its  appearance  and  gradually 
increased  until  1919,  when  its  tonnage  approximated  that  of  Trini- 
dad asphalt. 


V  PRODUCTION  OF  PETROLEUM  ASPHALTS  99 

The  petroleum  first  known  in  the  United  States  was  derived 
from  the  Pennsylvania,  Ohio  and  Indiana  fields.  This  was  of  the 
paraffin  type,  and  when  distilled  it  left  a  viscous  residue,  more  or 
less  asphaltic  in  character,  which  was  used  principally  to  flux  the 
harder  native  asphalts.  This  flux  could  not  be  distilled  to  a  solid 
without  decomposition  and  the  formation  of  coke.  In  1894  Byerley 
was  granted  a  patent  for  converting  these  fluxes  into  semi-solid  resi- 
dues by  blowing  air  through  them  at  high  temperatures,  thus  per- 
mitting them  to  be  used  without  admixture  for  most  purposes, 
although  they  never  met  with  much  favor  in  the  paving  industry. 
Upon  the  discovery  of  petroleum  in  California  it  was  possible  to 
obtain  semi-solid  to  solid  residual  asphalts,  closely  resembling  the 
native  asphalts,  and  suitable  for  use  in  the  construction  of  pave- 
ments. In  1902,  petroleum  asphalts  found  their  way  on  the  market 
in  appreciable  quantities,  about  20,000  tons  having  been  produced 
in  that  year.  By  1911,  the  tonnage  of  domestic  petroleum  asphalts 
exceeded  the  importations  of  Trinidad  and  Bermudez  asphalts  com- 
bined, and  from  that  time  on  the  production  of  petroleum  asphalts 
rapidly  increased.  In  1913  large  quantities  of  Mexican  petroleum 
asphalt  found  their  way  into  the  United  States  and  rapidly  increased 
until  in  1918  it  exceeded  the  domestic  production.  Since  1922, 
asphalt  produced  from  Venezuela  petroleum  has  been  produced  in 
rapidly  increasing  quantities,  followed  in  1925  by  asphalt  derived 
from  Colombian  petroleum. 

At  the  present  time  petroleum  asphalt  far  outranks  other  as- 
phalts in  importance.  In  1935  the  total  tonnage  of  petroleum 
asphalt  was  almost  ten  times  that  of  native  asphalts  and  related 
substances.  Of  the  total  production,  approximately  60  per  cent 
was  reported  as  having  been  derived  from  domestic  crude  petro- 
leum, and  40  per  cent  from  foreign  crudes,  including  Venezuelan, 
Mexican  and  Colombian  petroleum. 

Table  XI  shows  the  production  of  petroleum  asphalts  by  va- 
rieties in  the  United  States  in  1935,  divided  into  two  classes — solid 
and  semi-solid  products  of  less  than  200  penetration  and  semi-solid 
and  liquid  products  of  more  than  200  penetration.  The  major  por- 
tion of  the  latter  class  is  known  by  the  general  term  "flux,"  which 
as  the  name  implies,  is  used  mainly  as  a  blending  material  for  the 
harder  grades  and  also  for  blowing  purposes. 


100 


ANNUAL  PRODUCTION  OF  BITUMINOUS  SUBSTANCES 


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103 


TABLE  X 

PRODUCTION  BY  VARIETIES  IN  THE  UNITED  STATES  OF  NATURAL  ASPHALTS,  ASPHALTITES, 
ASPHALTIC  PYROBITUMENS  AND  PETROLEUM  ASPHALT  (1900-1935) 

(In  Short  Tons  of  2000  Ib.) 


Year 

Natural 
Asphalts 

Asphaltites 

Asphaltic 
Pyro- 
bitumens 

Total 
Natural 
Asphalts, 
Asphalt- 
ites and 
Asphaltic 
Pyro- 
bitumens 

Petroleum  Asphalts 

Gilsonite 

Grahamite 

Wurtzilite 

From 
Domestic 
Petro- 
leum 

From 
Foreign 
Petroleum 

Total  Do- 
mestic and 
Foreign 

1900 
1901 
1902 
1903 
1904 
1905 
1906 
1907 
1908 
1909 

54,389 
63,134 
84,632 
55,o68 
64,167 
62,898 
73,o62 
85,913 
78,565 
99,o6i 

20,826 
46,187 
44,405 
52,369 
64,997 
137,948 
119,817 

J  29,594 

20,826 
46,187 
44,405 
52,369 
64,997 
137,948 
119,817 

129,594 

59,639 
49,982 
58,163 
64,240 
57,296 
66,278 

2,978 
10,916 

12,447 
20,285 

18,533 
28,669 

1,000 
1,500 

I)9H 

966 
2,286 
3,894 

550 
500 
500 
422 
450 

220 

1910 
1911 
1912 

1913 
1914 
1915 
1916 
1917 
1918 
1919 

70,061 
51,228 
55,236 
57,549 
51,071 
44,329 
63,172 

4i,9i9 
25,346 
53,589 

25,432(*) 
30,236 
31,478 
28,000(0) 
1  8,548(0) 
19,909(0) 
24,5H(*) 
33,549(*) 
30,848 
29,192(0) 

4,000  (a) 
5,000 
7,700  (a) 
6,500  (a) 
9,669 
10,863 

8,431 
4,618 

3,803  W 

5,ooo  (a) 

400  (a) 
610 
750  (a) 
700(0) 
600  (0) 
650  (0) 
2,360  (0) 
1,51  8  (ac) 

37  W 

5oo  (0) 

98,893 
87,074 
95,166 
92,604 
79,888 
75,751 
98,477 
81,604 
60,034 
88,281 

161,187 

277,192 

354,344 
436,586 
360,683 
664,503 
688,334 
701,809 
604,723 
614,692 

161,187 
277,192 
354,344 
551,023 
674,470 
1,052,821 
1,260,721 
1,347,422 
1,202,420 
1,289,568 

i  M,437 
313,787 
388,318 

572,387 
645,613 
597,697 
674,876 

1920 
1921 
1922 
1923 
1924 
1925 
1926 
1927 
1928 
1929 

132,353 
284,037 
298,047 
365,601 

525,831 
545,o6o 
672,750 
796,100 
760,497 
748,550 

56,204 
10,066 
29,693 
34,425 
35,907 
39,520 
42,190 
42,580 
47,023 
54,987 

9,940  (b) 
2,004 
41 

198,497 
296,412 
327,792 
400,236 
562,367 
584,850 
715,180 
839,040 
807,860 
804,027 

700,496 
624,220 
805,145 
995,654 
,158,456 
,206,700 
,245,160 
,525,420 
,930,536 
2,332,973 

1,045,779 
908,093 
1,242,163 
1,378,722 
1,920,915 
1,971,670 
2,213,310 
2,426,030 
2,298,848 
2,355,498 

1,746,275 

1,532,313 
2,047,308 
2,374,376 
3,079,371 
3,178,370 
3,458,470 
3,951,450 
4,229,384 
4,688,471 

305 
II 
210  (e) 

569  w 

270 
240 

360  Or) 

340  tt) 
490  (l) 

60 

1930 

1931 
1932 

1933 
1934 
1935 

664,871 
470,491 

3H,039 
285,070 

410,453 
3H,i09 

37,684 
32,763 
25,955 
28,029 

30,355 
33,227 

222 

129 

2I 
36 

ft 

702,777 

503,383 
340,019 

313,135 
440,808 

347,336 

1,403,552 

1,274,744 

i,"  5,547 
1,237,386 
1,444,846 
1,801,778 

1,824,089 
1,700,946 
1,359,372 
1,218,665 
1,395,650 
1,485,225 

3,227,641 

2,975,690 
2,47^,919 
2,456,051 
2,840,496 
3,287,003 

(a)  Estimated. 

(b)  Including  wurtzilite. 

(c)  Including  18  tons  ozokerite. 
(<f)  Including  37  tons  ozokerite. 
(c)  Including  10  tons  ozokerite. 


(/)  Including  300  tons  ozokerite, 
(f )  Including  80  tons  ozokerite. 
(k)  Including  150  tons  ozokerite, 
(i )  Including  290  tons  ozokerite. 


104 


ANNUAL  PRODUCTION  OF  BITUMINOUS  SUBSTANCES 


TABLE  XI 

ASPHALT  AND  ASPHALTIC  MATERIAL  (EXCLUSIVE  OF  ROAD  OIL)  SOLD  AT  PETROLEUM 
REFINERIES  IN  THE  UNITED  STATES,  IN  1935,  BY  VARIETIES 

[Value  f.  o.  b.  refinery] 


From  Domestic 
Petroleum 

From  Foreign 
Petroleum 

Total 

Short 
Tons 

Value 

Short 
Tons 

Value 

Short 
Tons 

Value 

Solid  and  semisolid  products  of  less 
than  200  penetration:  * 
Asphalt  for: 
Paving  

4i9,77i 
303,234 
83,294 
3,i87 
37,674 
192 

6,212 
6,856 

47,749 

13,994,713 
3,170,647 
917,623 
40,663 
416,870 
1,718 
"3,3" 
75,9H 
500,746 

457,695 
328,138 
65,821 
",944 
3,271 
2,310 
1,728 
7,814 
56,836 

$4,805,877 
3,585,501 
703,7" 
136,081 
39,305 
25,393 
16,963 
85,016 
639,325 

877,466 
631,372 
i49,"5 
15,131 
40,945 
2,502 
7,940 
14,670 
104,585 

$8,800,590 
6,756,148 
1,621,334 
176,744 
456,175 
27,111 
130,274 
160,930 
1,140,071 

Roofing  

Waterproofing  

Blending  with  rubber  

Briquetting  

Mastic  and  mastic  cake  

Pipe  coatings  

Molding  compounds  

Miscellaneous  uses  

Total  

908,169 

67,393 
225.I9S 
3,736 

$9,232,205 

935,557 

45,673 
54,649 
24,074 
32 
329,899 
17,449 
8,528 
17,624 

$10,037,172 

1,843,726 

$19,269,377 

Semisolid  and  liquid  products  of 
more  than  200  penetration:  * 
Flux  for  — 
Paving  \ 

$581,032 
1,540,995 
58,480 

$432,539 
616,485 
299,767 
320 
3,481,445 
119,861 

83,321 
142,605 

113,066 
279,844 
27,810 
32 
707,953 
39,861 
20,744 
109,566 

$1,013,57! 
2,157,480 
358,247 
320 
7,409,279 
359,650 
245,941 
540,813 

Roofing  

Waterproofing  

Mastic  

Cut-back  asphalts  

378,054 
22,412 
12,216 
9i,942 

3,927,834 
239,789 
162,620 
398,208 

Emulsified  asphalts  and  fluxes  

Paints,  enamels,  japans,  and  lacquers 
Other  liquid  products  

Total  

800,948 

$6,908,958 

497,928 

$5,176,343 

1,298,876 

$12,085,301 

Grand  total,  1935  

i,709,H7 
1,353,639 

$16,141,163 
$13,973,765 

1,433,485 
1,373,602 

$15,213,515 
$15,921,674 

3,142,60^ 
2,727,241 

$31,354,678 
$29,895,439 

Total,  1934  

*  DEFINITIONS 

Paving  asphalt.*- Refined  asphalt  and  asphaltic  cement,  fluxed  and  unfluxed,  produced  for  direct  use  in  the  con- 
struction  of  sheet  asphalt,  asphaltic  concrete,  asphalt  macadam,  and  asphalt  block  pavements,  and  also  for  use 
as  joint  filler,  in  brick,  block,  and  monolithic  pavements. 

Roofing  a^>Aofc.— Asphalt  and  asphaltic  cement  used  in  saturating,  coating,  and  cementing  felt  or  other  fabric 
in  the  manufacture  of  asphalt  shingles. 

Waterproofing  asfhalt. — Asphalt  and  asphaltic  cement  used  to  waterproof  and  dampproof  tunnels,  foundations  of 
buildings,  retaining  walls,  bridges,  culverts,  etc.,  and  for  constructing  built-up  roofs, 

Briquetting  asphalt,— Asphalt  and  asphaltic  cement  used  to  bind  coal  dust  or  coke  breeze  into  briquets. 

Mastic  and  mastic  cake. — Asphalt  and  asphaltic  cement  for  laying  foot  pavements  and  floors,  waterproofing  bridges, 
lining  reservoirs  and  tanks,  capable  of  being  poured  and  smoothed  by  hand  troweling. 

Pipe  coatings. — Asphalt  and  asphaltic  cement  used  to  protect  metal  pipes  from  corrosion. 

Molding  compounds.— -AsphsAte  used  in  the  preparation  of  molded  composition,  such  as  battery  boxes,  electrical 
fittings,  push  buttons,  knobs,  handles,  etc. 

Miscellaneous  uses.— Asphalt  and  asphaltic  cement  used  as  dips,  and  in  the  manufacture  of  acid-resisting  com- 
pounds, putty,  saturated  building  paper,  fiber  board  and  floor  coverings,  and  not  included  in  the  preceding 
definitions. 

F/w*.— Liquid  asphaltic  material  used  in  softening  native  asphalt  or  solid  petroleum  asphalt  for  paving,  roofing, 
waterproofing,  and  other  purposes. 

Cut-back  asphalts. — Asphalts  softened  or  liquefied  by  mixing  them  with  petroleum  distillates. 

Emulsified  asphalt  and  ftuxes.~- Asphalts  and  fluxes  emulsified  with  water  for  cold-patching,  road  laying,  and 
other  purposes. 

Other  liquid  Products. ^?etTo\e\w  asphalt,  exclusive  of  fuel  oil  used  for  heating  purposes,  not  included  in  the  pre- 
ceding definitions, 


PRODUCTION  OF  ROAD  OIL  IN  THE  UNITED  STATES 


105 


ROAD  OIL  SOLD  BY  PETROLEUM  REFINERIES  IN  THE  UNITED  STATES,  1934-35, 

BY  DISTRICTS 


District 

I 

934 

19 

35 

Barrels 

Value 

Barrels 

Value 

_, 

938,053 

$1,392,665 

1,001,845 

$1,614,179 

88,195 

186,298 

34,035 

64,437 

1,984,414 

2,390,175 

1,957,569 

2,439,100 

Oklahoma-Kansas-Missouri  

942,072 

1,071,260 

597,450 

547,789 

Texas: 
Gulf  coast                         *  

204,888 

$274,188 

99,969 

$153,069 

Rest  of  State  

79,969 

79,963 

22,772 

35,775 

Total  Texas  

284,857 

$354,iSi 

122,741 

$188,844 

Louisiana-  Arkansas  : 

52,464 

$  9S,o89 

68,203 

$103,334 

157,992 

158,104 

384,769 

357,745 

Total  Louisiana  and  Arkansas  

210,456 

$253,193 

452,972 

$461,079 

1,023,434 

$1,431,920 

644,485 

$1,032,907 

California  

2,231,272 

3,662,336 

1,987,835 

2,194,621 

Grand  total                                 

7,702,753 

$10,741,998 

6,798,932 

$8,542,956 

106 


ANNUAL  PRODUCTION  OF  BITUMINOUS  SUBSTANCES 


PRODUCTION  OF  TARS  AND  PITCHES 

Tars  Derived  from  Coal.  By  far  the  most  important  source  of 
tar  produced  in  the  United  States  is  derived  from  bituminous  coal. 
The  following  represents  the  production  in  United  States  gallons : 2 


TABLE  XII 


Gas  Works 
(Horizontal,  Vertical 
and  Inclined) 

Coke  Ovens 
(All  Types) 

Water  and 
Oil  Gas 

1904 

42  million 

28  million 

9  million 

1908 

58 

43 

9 

1912 

4i 

94 

34 

1916 

50 

1  80 

55 

1918 

53 

263 

IOI 

1919 

53 

289 

105 

1920 

5i 

361 

116 

1921 

50 

^53 

109 

1922 

48 

328 

104 

1923 

48 

441 

1924 

48 

422 

108 

1925 

49 

480 

1926 

50 

529 

105 

1927 

51 

547 

1928 

5* 

632 

no 

1929 

47 

681 

117 

1930 

602 

1931 

45i 

1932 

50  to  40  (est'd) 

304 

1  10  to  80  (est'd) 

1933 

363 

1934 

409 

1935 

40  (est'd) 

468  (est'd) 

85  (est'd) 

No  statistics  are  available  giving  the  production  of  the  corre- 
sponding types  of  pitch. 

Tars  and  Pitches  Derived  from  Wood.  The  following  figures 
have  been  reported  by  the  U.  S.  Department  of  Commerce : 8 


Wood  Tar 
(gallons) 

Wood-tar  Pitch 
(tons) 

ion           

5,  <oo,ooo 

iqa<  

9,000,000 

13,500 

TQ27      

8,500,000 

10,000 

IQ2Q  

10,500,000 

4,500 

PRODUCTION  OF  MANUFACTURED  PRODUCTS 


107 


Other  Tars  and  Pitches.  There  are  no  published  figures  giving 
the  annual  production  of  other  tars  and  pitches  in  the  United  States. 
The  following  estimates  have  been  compiled  by  the  author  as  a  mere 
approximation  of  what  he  believes  to  be  their  present  relative 
standing. 

Tons  Annually 

Rosin  pitch 20,000  to  30,000 

Fatty-acid  pitch 15,000  to  20,000 

Blast-furnace  tar  and  pitch 5,ooo  to  10,000 

Bone  tar  and  bone-tar  pitch 2,000  to    5,000 

Shale  and  lignite  tars  and  pitches 250  to      500 


MANUFACTURED  PRODUCTS 

Bituminous  Paving  Materials.  The  total  tonnage  of  all  types 
of  asphalt,  including  asphalt  cements,  fluxes,  cut-back  asphalts,  emul- 
sified asphalts  and  liquid  residual  asphaltic  products  used  for  high- 
way purposes  in  the  United  States  have  been  reported  as  follows : 4 

Year  Tons 

1925 1,764,700 

1926 1,800,180 

1927 2,179,100 

19^8 2,487,642 

'9*9 , 2,655,989 

J930 2,693,552 

I9JI 2,901,851 

J932 2,838,344 

1933 2,500,110 

J934 2,977,990 

1 935 3,225,000 

The  mileage  of  improved  roads  completed  and  under  construc- 
tion as  of  January  ist  of  the  current  year  has  been  estimated  to  be 
as  follows : 5 


/ 

1935 
Miles 

1936 

Miles 

1937 

Miles 

Sand-clay  treated  

A  O7O 

7CO2 

c  60  £ 

Gravel  treated   

T-jW" 

22  8ol 

OVA 
0*7  72  C 

jiuwj 

A  7  IQA 

Macadam  treated  

•*-*,°yj 

11  66d. 

•*  /,/^J 
2A  6l  C 

^•J,1^ 
17  7C6 

Low-cost  bituminous  mixture  

»)  *  yj^'*r 
11.I2O 

•*4,UJ3 
on  8*72 

*  hi  Ov 

AC    fff 

Bituminous  macadam  

I6.CQ7 

jy,"  /•* 
16,466 

*TJ9JJJ 

i6.c<< 

Bituminous  concrete  

IQ.7I7 

II  C72 

ii  <8^ 

*  w>  /  *  / 

1  *O  /* 

*  *OW«> 

108 


ANNUAL  PRODUCTION  OF  BITUMINOUS  SUBSTANCES 


Bituminous  Roofing  Products.  Table  XIII  compiled  from  sta- 
tistics furnished  by  the  Asphalt  Shingle  and  Roofing  Institute,  New 
York  City,  and  the  U.  S.  Department  of  Commerce,  Washington, 
D.  C,  show  the  sales  of  asphalt  roll-roofings  and  asphalt  shingles 
in  the  United  States  from  1917  to  1936. 

TABLE  XIII 
SHIPMENTS  IN  "  SALES"  SQUARES— TOTAL  INDUSTRY  U.  S.  A. 


Year 

Smooth-roll 
Roofings 

Slate-roll 
Roofings 

Strip 
Shingles 

Individual 
Shingles 

Total 
All  Types 

1917 

21,252,000 

4,134,000 

1,266,600 

1,625,000 

28,277,000 

1918 

19,250,000 

4,312,000 

1,017,000 

1,149,000 

25,728,000 

1919 

16,930,000 

6,428,000 

2,311,600 

2,183,000 

27,952,600 

1926 

I7,579,ooo 

6,624,000 

2,253,900 

1,866,000 

28,322,000 

1921 

13,992,000 

7,670,000 

2,865,230 

1,632,000 

26,159,230 

1922 

14,604,000 

9,252,000 

4,243,630 

2,395,ooo 

30,494,630 

1923 

12,558,000 

9,847,000 

5,602,150 

2,492,000 

30,499,150 

19214. 

11,951,450 

10,608,100 

6,707,950 

3,103,000 

32,570,506 

1925 

11,990,709 

10,529,521 

7,803,202 

3,406,975 

33,730,4H 

1926 

13,502,977 

11,061,229 

8,529,382 

3,209,728 

36,303,316 

1927 

14,783,909 

10,798,454 

9,810,918 

2,582,031 

37,975,312 

1928 

16,074,654 

9,608,380 

9,002,297 

1,854,393 

36,539,724 

1929 

17,896,549 

9,989,787 

9,959,382 

2,015,781 

39,861,499 

1930 

I2,359,4H 

7,147,670 

6,820,775 

1,546,238 

27,874,097 

i93i 

10,794,478 

5,563,338 

4,887,134 

i,3i9,752 

22,564,702 

1932 

",996,723 

5,493,513 

4ii43ii33 

1,130,522 

22,763,891 

1933 

13,837,632 

5,684,905 

4,223,069 

991,547 

24,737,153 

1934 

12,837,702 

5,489,467 

4,422,486 

1,255,346 

24,005,001 

*935 

12,485,950 

6,426,369 

5,350,006 

1,787,826 

26,050,151 

1936 

15,251,646 

8,005,678 

6,851,860 

2,118,724 

32,227,908 

PRODUCTION  OF  MANUFACTURED  PRODUCTS 


109 


The  statistics  in  Table  XIV  have  been  compiled  by  the  U.  S. 
Department  of  Commerce,  Washington,  D.  C. : 6 

TABLE  XIV 
PRODUCTS,  BY  KIND,  QUANTITY  AND  VALUE,  1929,  1931  AND  1935 


Kind 

1935 

1931 

1929 

Roofing,  built-up  and  roll;  asphalt  shingles;  roof  coatings 
other  than  paint,  all  products  

$76,172,740 

$58,962,919 

$J03,  506,090 

Roofing  

70,589,616 

49»453»352 

Other  products  (not  normally  belonging  to  the  industry)  .  . 
Receipts  for  contract  and  custom  work  

5,517,081 
66,043 

9,509,567 

8,914,512 

Roofing,  built-up  and  roll,  asphalt  shingles,  and  roof  coat- 
ings other  than  paint,  made  as  secondary  products  in 
other  industries  

3,434,376 

6,143,744 

Asphalt  roll  roofing: 
Total  roofing  squares  

22,331,481 

17  I?2I\  143 

Total  value  

$24,768,468 

$20,272,517 

$36,109,653 

Smooth-surfaced  : 
Roofing  squares  

14,373,813 

II  659  193 

Value  

$13,710,544 

$11  213,050 

Grit-surfaced: 
Roofing  squares  

7,957,668 

Value  

$11,057,924 

<tg'Ocg'  467 

«  ?     '  Z2 

Asphalt  shingles: 
Total  roofing  aquares  

7,731,034 

6558524 

Total  value  

$26,801,952 

$22,566,749 

$42,291,343 

Strip: 
Roofing  squares  

6,048,383 

S2o6  2  ?Q 

Value  

$21,897,294 

$18  328  528 

9,692,774 

Individual  : 
Roofing  squares  

1,682,651 

I  352  265 

33,707,3  4 

Value  

$4,904,658 

&A  238  221 

£88 

Saturated  felt: 
Total  tons  

298,219 

143.  CT2 

3,  5 

Total  value  

$8,042,840 

$6,025,401 

2O5j525 
$9,803,629 

Asphalt-saturated  felt: 
Tons  

271,241 

IIO  727 

Value  

$6,237,267 

$4  68<  83^ 

A/-  £*      S 

Tar-saturated  felt: 
Tons  

26,978 

32  785 

f&  A(\C\ 

Value  

$1,805,573 

$i  339  566 

00,499 

Waterproofing  fabrics,  value  

$400,417 

(a) 

v3»  7  »* 

Roof-coatings  and  cements,  total  value  

NP*frV/v,,<t      / 

$6,374,359 

$4,298,946 

$6,311,449 

Asphalt  roof  cement  (solid)  : 
Tons  

106,790 

16  630 

Value  

$1,420,651 

$333  7  CO 

eo 

Coal-tar  roofing  pitch: 
Tons  

1 

Value                             

$808,808 

I           (&) 

(a) 

Fibrous  plastic  roof-cement: 

31  460  O42 

29,488,86l 

Value  

$1,176,998 

$1,347,599 

$2  336  III 

Fibrous  liquid  roof-coating: 
Gallons  .     .           

4,88l,023 

4,979,oi3 

4  O4I   ^63 

Value              

$1,928,595 

$2,040,783 

$2  II1?  *!78 

Nonfibrous  liquid  roof-coating: 

1,420,622 

I  O3I  260 

Value                             

$040.217 

$1-76.814 

$1  OI7  34O 

Other  roofing  materials  value  

S6.383.  41  7 

$2.433  483 

$6  168  787 

Asphalt  brick  siding: 

m_7«O 

1           t  \ 

Value            

"^ 
$1,243,539 

}       (a) 

(a) 

(a)  No  data. 


110 


ANNUAL  PRODUCTION  OF  BITUMINOUS  SUBSTANCES 


TABLE  XIV— Continued 
PRODUCTS,  BY  KIND,  QUANTITY  AND  VALUE,  1929,  1931,  1933  AND  1935 


Kind 

Year 

Quantity 

Value 

1935 

Squares 
1,171,095 

$5,234,727 

J933 
1931 
1929 

J93S 

408,256 
565,997 
894,164 
890,854 

1,826,279 
3,266,054 
5,277,308 

C67.QII 

Asphalt  roll  roofing  (c)  

1935 

22,331,481 

24,768,468 

Asphalt  shingles  (d)  

1933 
I93i 
1929 

1935 

12,333,342 
17,525,143 
28,437,076 

7,731,034 

12,763,519 
20,272,517 
36,109,653 

26,801,952 

Asphalt  and  tar  saturated  felt  (d)  

1933 
i93i 
1929 

1935 

4,008,811 

6>558,524 
11,676,636 
Tons  (2000  Ibs.) 
298,219 

11,994,618 

22,566,749 
42,291,343 

$8,042,840 

Clay  roofing  tile  (e)  

1933 
i93i 
1929 

1935 

75,623 
143,5" 

205,525 
Squares 
253,951 

2,778,308 

6,025,401 
9,803,629 

1,145,434 

Concrete  roofing  tile  (f)  

1933 
i93i 
1929 

1935 

103,257 
285,253 

370,771 
Tons  (2000  Ibs.) 
(g) 

810,647 

3,125,175 
3,943,847 

(g) 

Steel  sheets,  corrugated  and  crimped  (h): 
Galvanized  

1933 
i93i 
1929 

IO^S 

11,971 
31,860 
137,052 
Tons  (2240  Ibs.) 

«e8.  S74. 

338,809 
862,197 
2,869,092 

27  611  766 

Not  galvanized  

1933 
1931 
1929 
1935 

243,542 
262,307 
306,423 
6,506 

15,922,000 
18,381,000 
26,363,000 

ex.2  O8l 

Wood  shingles  (*)  

1933 
1931 
1929 

TQ7  e 

2,338 
3,O26 
5,285 

Thousands 
3^26  ^18 

140,000 
175,000 
380,000 

10  ^^8  ^60 

Asphalt  roof-cement  (solid)  (c)  

1933 
1931 
1929 

IQ*< 

2,929,800 
2,713,972 
6,110,672 
Tons  (2000  Ibs.) 
106.700 

6,958,275 
4,993,708 
18,026,482 

I  A2O  6?I 

Fibrous  plastic  roof-cement  (c)  

1933 
1931 
1929 

1935 

io,373 
16,630 
35,i6i 
Pounds 

•sj  4.60.04.2 

255,471 

333,750 
842,420 

1.176.008 

Fibrous  liquid  roof-coating  (c)  

1933 
1931 
1929 

IO"*«{ 

13,968,939 
29,488,861 

52,753,395 

Gallons 
A  881  02  * 

*»*/w,yyo 
661,044 

1,347,599 

2,336,111 

i  028  <co< 

Nonfibrous  liquid  roof-coating  (c)  

1933 
I93i 
1929 

1935 

3,003,734 
4,979,oi3 
4,941,563 

3,424,671 

1,011,323 
2,040,783 
2,115*578 

O4.O.2I7 

1933 
1931 
1929 

799,844 
1,420,622 
1,931,269 

183,729 
576,814 
1,017,340 

(a)  Made  in  the  Asbestos  Products  industry,  (b)  No  figures  available  for  earlier  years,  (c)  Made  principally 
in  the  Roofing  Materials  industry,  (d)  Made  in  the  Roofing  Materials  industry,  (c)  Made  in  the  Clay  Products 
industry,  (f)  Made  in  the  Concrete  Products  industry,  (g)  Not  yet  available.  (A)  Made  principally  in  the 
Steel  Works  and  Rolling  Mills  industry,  (h)  Made  in  the  Lumber  and  Timber  Products  industry. 


PRODUCTION  OF  MANUFACTURED  PRODUCTS 


111 


Asphalted  Felt-base  Floor  Coverings.  The  data  in  Table  XV 
have  been  compiled  by  the  U.  S.  Department  of  Commerce,  Wash- 
ington, D.  C. : 7 

TABLE  XV 

ASPHALTED  FELT-BASE  FLOOR  COVERING — PRODUCTS,  BY  KIND,  QUANTITY  AND  VALUE 


1935 

1931 

I929 

Total  square  yards  

128,041,256 

87,575,642 

117  060  72  C 

Total  value  

t3I>*S9>943 

$21,628,899 

$36,943,057 

Piece  goods: 
Total  square  yards  

66,610,504 

48,401,10 

57.O26  l6o 

Total  value  

$  1  4,46  1,  266 

$11,341,150 

$I4,68O,OI7 

12/4  and  wider: 
Total  square  yards  

2O.7O4.420 

5.2IO.5QO 

6  060  cci 

Total  value  

$4,412,620 

$1,227,276 

u>yv-n-'o$j 
$2,032,865 

Made  on  less  than  .050-!  nch-gauge  felt: 
Square  yards  

1  2.  11O.OO  5 

2.444.084 

2  1  60  III 

Value  

$2,448,780 

$5O2.Q1O 

^,iuy,i  1  1 
$  Coo  821 

Made  on  .O5o-inch-gauge  felt  or  thicker: 
Square  yards.'  

8,374,424 

2,76C,6o6 

f  jvy^ojii. 
4.7QI.442 

Value  

$I.Q6l.8lI 

$724.146 

$1   C21  OA.A. 

8/4: 
Total  square  yards  

4.1.766.061 

l8,886,OQ6 

»'A>J<*J>WT^ 

44  4OO  278 

Total  value  

19,53!,  5^4 

$9,110,304 

$11,621,078 

Made  on  less  than  .050-1  nch-gauge  felt: 
Square  yards  

24,644,42  5 

22,824,070 

2  1.8OO.2O1 

Value  

$5,124,065 

$4.<84.784 

$C~d.7O  6l2 

Made  on  .O5o-i  nch-gauge  felt  or  thicker: 
Square  yards  

10,121,618 

l6,o6l,II7 

fjrr/^yJjA 
2O  COO  08  C 

Value  

$4.4O7.45Q 

$4,525,520 

't'^'9jy^J)yQj 
$6  I  CO*AA6 

Narrower  than  8/4: 
Total  square  yards  

2,l6o,IO2 

4.1O4.47I 

f>V/,l^W^J.^.V 

C  66  C  C2O 

Total  value  

$517,122 

$1,003,570 

$1,026,074 

Made  on  less  than  .O5o-inch-gauge  felt: 
Square  yards  

1,224,071 

1,658,007 

C.4Q4  6  CO 

Value              

$285.804 

$807  1  06 

$06  c  87^1 

Made  on  .050-!  nch-gauge  felt  or  thicker: 
Square  yards    

Ol6  O2Q 

645  474 

ryuj>°/4 
I7O  87O 

Value  

$231,228 

4  1  06  464 

1  /U,O  /U 

26o  2OO 

Rugs: 
Total  square  yards  

6l,4l2,662 

10.  1  74  48C 

J>UV)4VAJ 

60  QAl  l6c 

Total  value  

$16,798,677 

$10,287,749 

uw>y4J,JuJ 
$22,263,040 

Made  on  less  than  .050-1  nch-gauge  felt: 
Square  yards  

11  741.412 

2  C.148  .060 

27  2QO.1O1 

Value  

28.142.774 

$5,76o,542 

^/j^^y  >owj 
$7.758,888 

Made  on  .050-1  nch-gauge  felt  or  thicker: 
Square  yards  .  »  •  

27.671  .2  CO 

11.826,425 

11.644.062 

Value  

$8,455,QO1 

$4.527.207 

$14,504.152 

PART  II 

SEMI-SOLID  AND  SOLID  BITUMENS  AND 
PYROBITUMENS 


CHAPTER  VI 
METHODS   OF  MINING,  TRANSPORTING  AND   REFINING 

MINING  METHODS 

Three  general  methods  are  followed  in  mining  semi-solid  and 
solid  bituminous  substances,  depending  upon  the  nature  of  the 
deposit. 

Open-cut  Quarrying.  Deposits  at  or  near  the  surface  are  mined 
by  simple  quarrying  methods.  If  exposed  on  hillsides,  the  rock 
asphalt  is  blasted  loose  and  loaded  on  railroad  cars  by  means  of 
steam  shovels  or  buckets  running  on  a  cable  way.  Deposits  located 
beneath  flat  terrain  are  mined  by  open  cuts,  after  first  removing  the 
overburden,  as  illustrated  in  Figs.  46  and  49.  The  asphalt  may  be 
hauled  from  the  cut  by  means  of  buckets  suspended  from  an  over- 
head cable  way,  or  by  dump-cars  pulled  up  inclined  tracks  on  cables. 

Tunnelling.  Veins  situated  a  distance  beneath  the  surface  are 
mined  by  tunnelling  methods,  which  also  adapt  themselves  to 
handling  veins  filling  hillside  faults  or  fissures.  Typical  tunnelling 
methods  are  illustrated  in  Figs.  64  and  69.  Horizontal  veins  may 
be  handled  by  pit-and-stall  methods  if  the  overlying  stratum  is  solid 
enough  to  resist  caving  in,  otherwise  the  roof  and  possibly  also  the 
sides  of  the  tunnel  must  be  timbered,  which  of  course  adds  to  the 
cost  of  mining,  Asphaltites  are  generally  mined  in  this  manner. 

Special  Methods.  Asphalts  deposits  occurring  in  the  form  of 
so-called  lakes,  as  for  example  at  Trinidad  and  Bermudez,  are  mined 
by  comparatively  crude  methods,  involving  the  use  of  the  pick  and 

shovel,  as  illustrated  in  Figs.  43  and  59.    The  asphalt  is  dumped 

112 


VI 


METHODS  OF  SHIPMENT  AND  TRANSPORTATION 


H3 


by  hand  in  small  cars  on  a  movable  track,  whence  it  is  transported 
to  the  main  railroad  line  or  to  steamers,  if  near  the  seacoast. 

METHODS  OF  SHIPMENT  AND  TRANSPORTATION 

Hard  rock  asphalts  and  asphaltites  are  shipped  in  fragments, 
either  in  bulk  the  same  as  coal,  or  if  the  material  is  of  sufficient 
intrinsic  value  to  warrant  the  expense,  it  may  be  shipped  in  sacks 
weighing  150  to  200  Ib.  each.  Where  intended  for  constructing 
asphalt  mastic  pavements  or  floors,  the  rock  asphalt  is  cast  in  the 


Courtesy  Atlantic  Refining  Co. 
FIG.  35. — Tank-cars  Used  for  Transporting  Asphalt. 

form  of  flat  cakes  weighing  between  50  and  75  Ib.  for  the  con- 
venience of  handling. 

If  the  asphalt  is  comparatively  free  from  mineral  matter,  and 
this  applies  also  to  petroleum  asphalt,  it  may  be  shipped  in  six 
types  of  containers,  as  follows:1 

(i)  In  tank  cars  having  capacities  of  6500,  8000  and  10,000 
gal.  as  illustrated  in  Fig.  35.  These  are  provided  with  steam  coils 
for  remelting  the  asphalt  upon  arrival  at  destination,  and  are  prefer- 
ably insulated,  so  that  they  may  be  transported  in  a  melted  state 
with  the  minimum  loss  of  heat. 


114          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

(2)  Tank  trucks  equipped  with  heating  flues  in  which  a  fire  is 
maintained  by  an  oil  burner  during  transit.    These  are  generally 
used  for  transporting  asphalts  for  road  and  paving  purposes. 

(3)  Light  metal  drums  with  a  metal  top  having  a  6-in.  hole  in 
the  center  for  convenience  in  filling.    These  usually  weigh  475  to 
525  lb.,  holding  50  to  55  gal. 

(4)  Wooden  barrels  of  about  the  same  capacity  as  stated  in 
(3).     These  are  generally  used  for  transporting  liquid  to  semi- 
liquid  materials,  and  are  filled  at  the  lowest  temperature  to  prevent 
excessive  contraction  taking  place  upon  cooling. 

(5)  Fiber  barrels  and  other  containers,2  which  should  be  filled 
at  temperatures  lower  than  300°  F.    It  is  recommended  that  these 
be  lined  with  clay  to  prevent  adhesion  of  the  asphalt3  and  thus 
facilitate  stripping  off  the  container  when  used.     Other  products 
recommended  for  this  purpose  include  alkaline  sludge  obtained  as 
a  by-product  in  refining  petroleum  products,4  glycerol  foots,5  an 
aqueous  solution  of  oxalic  acid  or  sodium-hydrogen  phosphate  con- 
taining glycerol,6  etc, 

(6)  Molds  for  the  shipment  of  high  melting-point  asphalts, 
which  may  be  of  the  same  form  as  barrels.    These  are  filled  in  the 
same  manner  as  drums,  and  when  the  asphalt  has  cooled,  they  are 
opened  up  and  the  block  removed  and  shipped  as  such.7     The 
cakes  may  also  be  coated  with  a  high  fusing-point  asphalt  or  as- 
phaltite  (e.g.,  gilsonite).8    This  method  eliminates  the  payment  of 
freight  on  the  container,  but  only  adapts  itself  to  materials  which 
are  sufficiently  rigid  and  tough  to  withstand  shipment. 


METHODS  OF  REFINING 

Dehydration.  Most  native  asphalts  contain  more  or  less  mois- 
ture, which  may  be  present  either  accidentally  as  hydroscopic 
moisture,  or  in  the  form  of  an  emulsion.  Trinidad  asphalt  is  an 
'example  of  the  latter,  in  which  about  29  per  cent  of  water  is  emul- 
sified with  the  asphalt  and  clay. 

Before  the  asphalt  can  be  used  commercially,  this  water  or 
moisture  must  be  removed.  The  process  by  which  this  is  accom- 
plished is  known  as  "dehydration."  The  expulsion  of  water  is 
brought  about  by  heating  the  asphalt  in  a  suitable  open  container 
constructed  of  iron  or  steel,  which  is  built  in  two  types,  viz. : 

(1)  Semi-cylindrical. 

(2)  Rectangular. 


METHODS  OF  REFINING 


115 


In  either  case  the  top  is  left  open  so  that  the  water  may  be 
expelled  readily.  In  modern  plants,  the  heating  tanks  are  built  to 
contain  between  10  and  30  tons  of  the  crude  asphalt. 

The  heating  is  effected  by  various  means: 

( i )  By  direct  fire  heat,  in  the  form  of  a  combustion  chamber 
underneath  the  tank,  enclosed  in  fire  bricks.  Three  kinds  of  fuel  are 
used  for  this  purpose,  depending  upon  which  is  most  readily  ob- 
tained in  the  locality  where  the  asphalt  is  to  be  refined;  namely, 
coal  or  coke,  oil,  or  gas.  Coal  is  burnt  on  a  grate ;  oil  is  usually 


FIG.  36. — Showing  Arrangement  of  Refining  Stills  for  Natural  Asphalt. 

sprayed  into  the  combustion  chamber  by  compressed  air  or  steam ; 
and  natural  or  producer  gas  is  introduced  through  a  suitable  type 
of  burner.9  In  any  case,  the  best  practice  consists  in  protecting 
the  bottom  of  the  melting-tank  by  a  fire-brick  arch  work,  so  that 
the  hot  gases  are  compelled  to  circulate  back  and  forth.10  This 
subjects  the  bottom  of  the  tank  to  a  more  uniform  temperature,  and 
tends  to  prolong  its  life.  At  the  same  time,  it  economizes  fuel  by 
more  thoroughly  extracting  the  heat  from  the  hat  gases,  due  to  the 
increased  area  of  contact  with  the  bottom  of  the  tank.  Some  recom- 
mend the  use  of  a  perforated  brick  arch  to  distribute  the  hot  gases 
uniformly  and  prevent  the  bottom  of  the  tank  from  being^  over- 
heated locally.  Fire  melting-tanks  are  usually  semi-cylindrical  in 
form,  although  sometimes  they  may  be  rectangular  at  the  top,  with 
a  semi-cylindrical  bottom. 


116          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

(2)  By  means  of  steam.  In  this  case  the  heating  is  effected  by 
coils  of  steam  pipes  contained  in  the  tank.  One  and  one-quarter  to 
i^-in.  pipes  are  generally  used  for  this  purpose.  According  to  the 
best  practice,  these  are  bent  in  coils  composed  of  a  continuous 
length  of  pipe  without  unions  or  joints,  as  illustrated  in  Fig.  36. X1 
Another  method  consists  in  using  cast-iron  headers  with  straight 
lengths  of  1^4  or  i  ^-in.  pipes  fastened  in  between.  Steam  is  used 
at  pressures  between  125  and  150  Ib.  This  will  raise  the  tempera- 
ture of  the  asphalt  to  300  or  400°  F.  Steam  has  the  advantage 
over  fire  heat  in  not  coking  the  asphalt,  which  would  tend  to  insu- 
late the  bottom,  induce  local  overheating,  and  burn  out  the  tank  in 
a  comparatively  short  time. 


Courtesy  of  Parks  Cramer  Co. 
pIG.  37. — Hot  Oil  Circulation  Method  for  Heating  Asphalts. 

(3)  Electrical    Immersion   Heaters.12     Electric   heating   units 
contained  in  a  series  of  ic-in.  pipes  (closed  at  both  ends)  are  placed 
at  the  bottom  of  the  tank.     Each  unit  has  a  capacity  of  54  k.W. 
and  serves  to  heat  the  air  in  the  pipe,  which  in  turn  imparts  its 
heat  to  the  surrounding  asphalt.     This  same  device  has  been  uti- 
lized for  saturating  roofing  felt,  in  which  case  the  asphalt  is  main- 
tained at  440°  F.  while  the  felt  is  being  treated  at  the  rate  of  I  ton 
per  hour,  which  corresponds  to  a  heat  consumption  of  about  10,000 
B.t.u.  per  hour  per  ton  of  asphalt. 

(4)  By  contact  with  molten  metals  or  alloys.     Another  pro- 
cedure consists  in  promoting  the  rapid  heating  of  the  asphalt  by  a 
bath  of  molten  lead,  tin,   zinc,   or  various   alloys  of  low  fusing- 
point.18 


VI  METHODS  OF  REFINING  117 

(5 )  By  hot  oil  circulation.    This  is  accomplished  by  circulating 
heated  mineral  oil  of  a  high  flash-point  through  a  closed  system  of 
pipes,  including  a  heating  coil  in  the  asphalt  melting  tank  and  a 
second  coil  located  in  a  furnace  situated  a  short  distance  away  from 
the  tank.     The  second  coil  is  heated  by  means  of  an  oil  or  gas 
burner,  which  by  means  of  a  thermostatic  control  serves  to  heat  the 
oil  to  a  predetermined  temperature,  usually  at  550  to  600°  F.    Fig. 
37  illustrates  the  oil  heater  and  circulating  pump.14 

(6)  By  means  of  diphenyl  vapor.     Dbhenyl  is  a  white  solid, 
melting  at  156.6°  F.  and  boiling  at  491.5°  F.  under  a  pressure  of  I 
atmosphere.     At  491.5°  F.  it  has  a  pressure  of  14.7  Ib.  absolute 
and  at  600°  F.  it  has  a  pressure  of  only  47  Ib.     In  view  of  these 
properties,  its  use  has  been  promoted  for  heating  asphalts,  etc.15    A 
mixture  of  diphenyl  and  diphenyl  oxide  has  also  been  proposed,16 
likewise  naphthalene. 

(7)  By  circulating  the  asphalt  itself.17    This  is  a  modification  of 
the  preceding  method,  in  which  the  mineral  oil  is  replaced  by  the 
asphalt  which  is  to  be  heated.     In  this  case  the  heating  coil  in  the 
asphalt  melting  tank  is  omitted,  and  the  asphalt  is  pumped  directly 
from  the  bottom  of  the  tank  through  a  heating  coil  in  the  outside 
furnace,  and  then  back  again  into  the  melting  tank.    The  heating 
coil  is  brought  to  the  proper  temperature  (which  may  be  controlled 
thermostatically)    by  oil   or  gas   combustion.     This  procedure^  is 
simple  and  efficient,  but  adapts  itself  only  to  asphalts  having  a  high 
flash-point  and  which  are  substantially  free  from  mineral  matter  or 
other  ingredients  which  will  settle  in  the  coils  and  induce  carboniza- 
tion.    The  asphalt  must  also  be  free  from  water  and  capable  of 
being  heated  rapidly  without  frothing. 

The  time  of  heating  can  be  reduced  materially  by  agitating  the 
asphalt  mechanically,  since  the  transfer  of  heat  through  a  mass  of 
asphalt  is  very  slow.  The  agitation  may  be  Accomplished: 

(a)  By  jets  of  dry  steam  which  should  be  introduced  after  the 
temperature  of  the  asphalt  becomes  sufficiently  high  to  prevent  con- 
densation, and  thus  avoid  excessive  foaming.18 

(b)  By  jets  of  air. 

(c)  By  mechanical  agitators. 

During  the  process  of  dehydration,  the  mass  is  apt  to  froth  when 
the  temperature  is  raised  beyond  the  boiling-point  of  water.  For 
this  reason,  it  is  well  to  build  the  tanks  large  enough  to  accommo- 
date the  foam  without  danger  of  overflowing.  Shallow  tanks  are 
preferable  to  deep  tanks. 


118          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

Certain  types  of  asphalt  are  most  difficult  to  dehydrate,  as  they 
foam  very  badly.  Numerous  devices  have  been  used  to  keep  down 
the  foam,  the  simplest  and  most  successful  consisting  in  directing  a 
current  of  hot  air  against  the  surface  of  the  asphalt  while  it  is  being 
melted. 

The  use  of  steam  accelerates  the  evaporation  of  the  more  vola- 
tile constituents  in  the  asphalt,  and  is  therefore  apt  to  cause  a 
greater  shrinkage  during  the  dehydration  than  when  air  or  mechani- 
cal mixing  is  used.19  On  the  other  hand,  air  is  apt  to  "oxidize"  the 
asphalt  and  increase  its  fusing-point,  especially  if  its  use  is  con- 
tinued for  long  periods  of  time. 

Sometimes  the  asphalt  is  subjected  to  a  process  of  partial  distilla- 
tion in  a  closed  retort  to  remove  the  volatile  constituents  and  raise 
its  fusing-point,  which, 'however,  is  stopped  before  the  formation  of 
carbonaceous  matter.20  A  modification  consists  in  adding  a  propor- 
tion of  vegetable  oil  during  the  refining  process  for  the  purpose  of 
absorbing  the  sulfur  derivatives  loosely  combined  with  the  asphalt;21 

Any  impurities  such  as  vegetable  matter,  chips  of  wood,  etc., 
which  rise  to  the  surface  when  the  asphalt  is  melted  should  be 
skimmed  off.  When  the  asphalt  is  thoroughly  melted  and  the  foam- 
ing ceases,  the  dehydration  is  complete.  It  is  usually  unnecessary  to 
raise  the  temperature  of  the  asphalt  higher  than  350°  F.  The  de- 
hydrated asphalt  may  be  discharged : 

1 i )  By  a  valve  at  the  bottom  of  the  tank,  permitting  the  asphalt 
to  flow  out  by  gravity. 

(2)  By  a  rotary  pump  which  may  either  be  steam-jacketed22 
or  surrounded  by  a  steam  coil  in  close  contact  with  the  pump,  the 
entire  installation  being  well  insulated.    The  rotary  pump  is  usually 
installed  above  the  level  of  the  asphalt,  and  the  intake  pipe  extended 
almost  to  the  bottom  of  the  heating-tank. 

(3)  By  means  of  a  pneumatic  lift  installed  below  the  bottom  of 
the  tank.    The  asphalt  is  allowed  to  flow  by  gravity  into  the  pneu- 
matic lift,  which,  by  a  suitable  mechanism,  automatically  shuts  off 
the  flow  when  it  is  filled,  and  then  admits  compressed  air,  forcing 
the  asphalt  upward  through  the  discharge  pipe.    The  pneumatic  lift 
may  either  be  steam-jacketed  or  heated  with  a  steam  coil  as  de- 
scribed. 

(4)  By  means  of  an  Archimede's  screw,  which  serves  to  extrude 
asphalt  compositions  in  the  plastic  state.23 


VI 


METHODS  OF  REFINING 


119 


A  device  for  discharging  the  melted  asphalt  into  light  metal 
drums,  in  which  nine  are  filled  simultaneously,  is  illustrated  in 
Fig.  38. 

Asphalt  may  be  pumped  through  pipe  lines  for  distances  of  500 
feet  or  more.  To  effect  this  it  must  be  maintained  in  a  melted 
state.  This  is  accomplished  by  running  a  steam  pipe  of  small 


Courtesy  Atlantic  Refining  Co. 
FIG.  38. — Discharging  Melted  Asphalt  into  Drums. 

diameter  inside  the  pipe  carrying  the  asphalt.24     The  outer  pipe 

should  be  well  insulated. 

Hard  asphalts  are  first  pulverized  and  then  dried  in  air.25 
Distillation.     Attempts  have   also  been  made  to  utilize  rock 

asphalts  associated  with  a  small  percentage  of  bituminous  matter, 

and  which  cannot  be  utilized  for  other  purposes,  by  subjecting  them 


120          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

to  a  process  of  destructive  distillation  26  and  recovering  the  volatile 
products,  including  the  lubricating  oil  fraction,27  which  correspond 
closely  with  those  obtained  upon  distilling  pyrobituminous  shales. 


FIG.  39.— Jaw  Crusher. 

However,  the  low  market  price  of  petroleum  has  been  an  obstacle 
to  the  success  of  such  operations. 

Rock  asphalts  may  be  distilled  to  harden  same  for  use  in  paving 


FIG.  40. — Toothed-Roller  Crusher. 


impositions.28  If  coarse  or  undesirable  mineral  aggregate  is  pres- 
mt,  it  may  be  screened  to  the  desired  mesh  while  in  a  melted  state, 
ind  electrically  heated  screens  have  been  proposed  for  this  purpose. 


20 


VI 


METHODS  OF  REFINING 


121 


Comminution.  Natural  rock  asphalts  and  asphaltites  may  be 
comminuted30  in  three  different  types  of  apparatus,  including  jaw- 
crushers  illustrated  in  Fig.  39,  toothed  rollers  as  illustrated  in  Fig. 


FIG.  4IA. — Disintegrator  (Showing  Wheels  Separated). 


40,  and  a  disintegrator  as  illustrated  in  Figs.  41  (A)  (showing  the 
machine  taken  apart)  and  41(6)  (showing  the  machine  assembled). 
After  being  crushed  and  ground,  the  product  is  screened  to  the  re- 


FiG.  4iB.— Disintegrator  (Showing  Machine  Assembled). 

quired  mesh,  and  finally  heated  in  a  revolving,  fire-heated  cylinder  to 
expel  the  associated  moisture,  usually  at  a  temperature  of  260  to 
300°  F.  The  asphalt  content  of  the  comminuted  material  can  be 


122          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

adjusted  by  grinding  together  rock  taken  from  the  rich  veins  with 
material  mined  from  the  poorer  strata.  When  used  for  paving 
purposes,  the  product  is  usually  transported  directly  to  the  job 
while  it  is  still  hot.31 

Sedimentation.  This  process  is  used  to  separate  the  water  where 
it  is  present  in  substantial  quantities,  as  well  as  any  coarse  particles 
or  lumps  of  mineral  matter.  It  can  only  be  used  successfully  with 
asphalts  or  other  forms  of  bitumen  melting  below  the  boiling-point 
of  water  (212°  F.),  and  not  carrying  the  water  in  an  emulsified 
state.  The  asphalt  is  maintained  at  a  temperature  not  exceeding 
200°  F.  by  any  of  the  devices  described  under  "Dehydration,"  and 
allowed  to  undergo  a  process  of  sedimentation,  whereby  the  en- 
trained water  and  coarse  mineral  matter  settle  to  the  bottom,  leav- 
ing the  purified  asphalt  on  top.  The  latter  is  then  carefully  drawn 
off.32  Steam  heating  is  most  satisfactory  for  this  purpose. 

In  some  cases  only  a  portion  of  the  water  separates  by  sedimen- 
tation, whereupon  the  process  is  supplemented  by  one  of  dehydra- 
tion. The  sedimentation  will  remove  most  of  the  water  and  has 
the  advantage  of  materially  shortening  the  dehydration  process. 
A  combination  of  the  two  processes  will  thus  prove  more  effective 
than  the  use  of  either  one  alone. 

Since  water  usually  has  a  higher  specific  gravity  than  melted 
asphalt,  it  tends  to  settle  to  the  bottom  of  the  vessel  containing  it. 
This  invariably  proves  to  be  the  case  with  the  softer  forms  of  na- 
tive asphalt. 

Extraction.  Two  media  have  been  used  for  this  purpose,  namely 
water  and  volatile  solvents.  As  the  methods  are  entirely  different, 
they  will  be  considered  separately. 

Extraction  by  Means  of  Water.  This  method  has  been  used 
with  more  or  less  success  for  extracting  asphalt  from  asphaltic  sands, 
sandstone  and  limestone.  It  is  based  on  the  principle  that  water 
has  a  higher  specific  gravity  than  the  melted  asphalt,  and  a  lower 
gravity  than  the  accompanying  mineral  matter,  so  that  when  boiled 
together,  the  melted  asphalt  will  rise  to  the  surface  and  the  mineral 
constituents  settle  to  the  bottom.33  Calcium  chloride,84  sodium  car- 
bonate 85  and  salt ae  have  been  proposed  to  be  added  to  the  water 
to  increase  its  gravity  and  thereby  effect  a  more  thorough  separa- 


VI  METHODS  OF  REFINING  123 


tion  of  the  asphalt.     Rock  asphalts  after  weathering  yield  more 
difficultly  to  the  water-separation  process.87 

To  yield  successfully  to  this  method,  the  rock  asphalt  must  pos- 
sess the  following  characteristics: 

1 i )  The  asphalt  present  in  the  rock  should  have  a  fusing-point 
of  not  exceeding  90°  F.     (Test  150.) 

(2)  The  particles  of  mineral  matter  should  be  unconsolidated. 

3        C        rr\t          f  •  f  •  t  .,  1  111  £_•     1  ._      ,_ 


(3)  The  grains  of  mineral  matter  should  be  fairly  coarse  to 
enable  them  to  settle  rapidly. 

Experience  has  shown  that  when  the  fusing-point  of  the  asphalt 
contained  in  the  rock  is  higher  than  90°  F.,  boiling  water  will  not 
effect  a  thorough  separation. 

A  specimen  of  asphaltic  sand  obtained  near  Woodford,  Okla., 
carrying  approximately  12  per  cent  of  asphalt  and  88  per  cent  of 
sand  in  the  form  of  loose,  rounded  grains  between  40-  and  8o-mesh, 
separated  fairly  completely  on  boiling  with  water.  The  pure  asphalt 
showed  a  fusing-point  between  65  and  70°  F. 

Another  asphaltic  sand  obtained  near  Fort  McMurray,  in 
northern  Alberta,  carrying  approximately  15  per  cent  of  asphalt 
and  85  per  cent  of  non-compact  sand,  between  40-  and  loo-mesh, 
likewise  largely  separated  on  boiling  with  water.  The  fusing-point 
of  the  pure  asphalt  was  50°  F. 

The  same  was  true  with  an  asphaltic  sand  carrying  1 7  per  cent 
of  asphalt  obtained  from  a  deposit  46  miles  northwest  of  Edmon- 
ton, and  12  miles  north  of  Onoway.  In  this  case  the  pure  asphalt 
fused  at  62°  F. 

A  Mexican  asphaltic  sand  carrying  16  per  cent  of  asphalt  also 
separated  completely  on  boiling  with  water,  the  fusing-point  of  the 
pure  asphalt  being  78°  F. 

On  the  other  hand,  certain  asphaltic  sands  obtained  from  various 
localities  of  Oklahoma,  carrying  between  10  and  15  per  cent  of 
asphalt,  refused  to  separate  on  boiling  with  water.  The  fusing- 
points  of  the  pure  asphalts  were  found  to  be  113°  F.,  118°  F.,  and 
127°  F.,  respectively.  The  particles  of  the  sand  were  substantially 
similar  to  the  preceding,  ranging  between  40-  and  loo-mesh. 

Plants  for  the  water-extraction  of  asphalt  from  rock  asphalt 
have  been  in  operation  in  Oklahoma  (sand  asphalt) ;  Texas  (as- 
phaltic limestone) ;  Alberta,  Canada  (sand  asphalt) ;  Pechelbronn, 


124 


METHODS  OF  MINING,  TRANSPORTING  AND  REFINING 


VI 


Alsace-Lorraine  (asphaltic  limestone);  Seyssel  and  Bastennes, 
France  (asphaltic  limestone) ;  San  Valentino,  Italy  (asphaltic  lime- 
stone) ;  Tataros,  Austria  (asphaltic  limestone) ;  also  in  Russia 
(sand  asphalt). 

A  cross-sectional  diagram  of  an  apparatus  which  gives  fairly 
successful  results  is  shown  in  Fig.  42.  The  separated  asphalt  must 
be  treated  in  accordance  with  the  methods  described  under  the 
heading  "Dehydration/*  to  separate  the  water  which  is  mechanically 
carried  along  with  it  If  the  process  has  been  performed  properly, 
the  purified  asphalt  will  not  contain  more  than  5  to  7  per  cent  of 
mineral  matter.  The  water-extraction  process  also  is  used  for  puri- 


Perforateef  Metal  Plat* 
TO  allow  Wafer  to  dram  off 
separated  Asphalt 


iStirring  Dev 

\    Cham  with  diodes 
\to  carry  oft  separated 
asphalt 


Pure  Asphalt  Floats  on 
Surface  o 


Vo/res  to  draw  off'' 
Mtneral  Matter      ; 


Serrf/ngr  Chamber  for 
Mtneral  Matter 


FIG.  43. — Apparatus  for  Separating  Soft  Asphalt  from  Sand  by  Means  of  Water. 

fying  ozokerite  and  to  remove  water-soluble  constituents  (e.g.,  salt) 
from  certain  native  asphalts,  and  thereby  improve  their  weather- 
resisting  properties.38 

A  flotation  process  has  been  proposed,  which  consists  in  agitating 
the  sand  asphalt  at  60  to  80°  C.  with  a  o.i  per  cent  solution  of  a 
froth  former,  e.g.,  soda  ash,  alkaline  soap,  turkey-red  oil,  saponin, 
glue,  etc.;  the  aqueous  solution  being  then  separated  by  decantation 
and  the  mineral  matter  removed  by  lixiviation.80  The  use  of  ben- 
tonite  40  alkali  (e.g.,  NaOH  or  Na2CO3),41  sodium  phosphate,42  so- 
dium silicate,48  sodium  silicate  in  combination  with  calcium  chloride 
or  salt,44  sulfonated  mineral  oils,45  etc.,  have  also  been  suggested 
for  this  purpose. 


VI  METHODS  OF  REFINING  125 

Extraction  or  Precipitation  with  Solvents.  Carbon  disulfide, 
petroleum  distillates  and  benzol  have  been  used  for  this  purpose. 
This  method  has  not  proven  successful  commercially,  on  account  of 
its  expense.  Several  plants  have  been  constructed  in  the  United 
States  for  extracting  asphalts  from  asphaltic  sands  and  sandstone. 
The  Alcatraz  Asphalt  Co.  of  Alcatraz,  Cal.  (1896—1899),  erected 
an  elaborate  plant  for  treating  rock  carrying  10  to  16  per  cent  of 
asphalt.  The  venture,  however,  proved  a  failure  through  losses  in 
solvent  (a  light  distillate  of  petroleum),  which  made  the  cost  of 
treatment  prohibitive.  The  loss  was  due  in  part  to  unavoidable 
evaporation  during  the  extraction  process,  also  ,to  the  impossibility 
of  fully  recovering  the  solvent  from  the  extracted  residue. 

Solvents  may  be  used  either  to  extract  solid  bituminous  sub- 
stances (e.g.,  rock  asphalts,  sand  asphalts,  certain  pitches,  etc.),  or 
to  precipitate  components  from  fluid  bituminous  substances  (e.g., 
petroleum,  tars,  etc.)  or  solutions  of  solid  bituminous  substances  in 
various  menstra.  The  following  classes  of  solvents  have  been  pro- 
posed for  these  purposes : 46 

(a)  Solvents  derived  from  petroleum: 

Crude  petroleum;47  liquid  ethane,  pentane,  propane  or  bu- 
tane;48 light  petroleum  distillates  (e.g.,  petroleum  ether,  gasoline, 
or  petroleum  naphtha)  ; 49  kerosene; 50  heavy  mineral  oils; 51  etc. 

(b)  Solvents  derived  from  coal  tar: 

Benzol;52  toluol;58  xylol  (solvent  naphtha);54  heavy  oils;55 
naphthalene ; 56  tetrahydronaphthalene  ( "tetralin" ) ; 57  nitroben- 
zene;58 benzonitrile ; 59  phenol;60  phenyl  nitrile;61  aniline;62  pyri- 
dine  or  quinoline. 

(c)  Solvents  derived  from  wood: 

Turpentine; 63  methyl  or  ethyl  alcohol; 64  higher  alcohols  (e.g., 
butyl,  isobutyl,  propyl,  iso-propyl,  amyl,  fusel  oils,  benzyl,  etc.)  ; 65 
acetone ;  6e  acetone  oils ; 67  wood  oils ; 68  furfural  or  methyl  furfural 
("furfural  process");69  glacial  acetic  acid;70  methyl  or  ethyl  ace- 
tate; 71  amyl  acetate;  crpton  aldehyde  ("Foster- Wheeler  process"). 

(d)  Sulfur  derivatives: 

Liquid  sulfur  dioxide  ("Edeleanu  process");72  carbon  disul- 
fide;73 sulfo-derivatives  of  mineral  oils  and  tars.74 

(e)  Sundry  solvents: 

Ethyl  ether ; 75  carbon  tetrachloride,  trichlorethylene,  ethyl ene 
dichloride,  or  dichlor-djethyl  ether  ("chlorex  process");  amine 
bases  (e.g.,  iso-amyl  amine,  di-iso-propyl  amine,  di-iso-butyl  amine, 
etc.).76 


126          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

(f)   Mixtures  of  solvents: 

Petroleum  naphtha  with  amyl  alcohol ; 77  pentane  with  butane, 
or  propane  with  ethane; 7S  propane  with  cresol  ("Dusol  process")  ; 
benzol  or  toluol  with  alcohols;79  benzol  with  acetone;80  benzol 
with  liquid  sulfur  dioxide  (uEdeleanu  process");  propane  with 
liquid  sulfur  dioxide;81  ethyl  alcohol  with  ethyl  ether;  methyl  for- 
mate with  benzol,  carbon  disulfide  or  carbon  tetrochloride ; 82  phenol 
with  a  polyhydric  alcohol ; 83  successively  with  alcohol,  or  acetone, 
petroleum  naphtha,  and  finally  with  benzol  or  toluol.84 

For  the  production  of  high-grade  lubricating  oils  from  heavy 
petroleum  fractions,  the  use  of  liquid  propane  as  a  solvent  (or 
more  accurately,  as  "antisolvent")  has  become  increasingly  popu- 
lar.85 The  following  constituents  present  in  ordinary  lubricating 
oil  fractions  must  be  eliminated,  viz. :  paraffin  wax  to  obtain  a  low 
pour-point,  asphalt  because  of  its  instability  and  excessive  carbon- 
forming  tendencies,  the  heavy  ends  of  the  lubricating  oils  because 
of  their  high  carbon-forming  tendencies,  naphthenic  compounds  of 
olefinic  or  aromatic  characteristics  because  of  their  low  stability  and- 
low  viscosity  index,  and  color  bodies  to  render  the  lubricating  oil 
more  marketable.  Refining  with  liquid  propane  makes  available  as 
by-products  a  whole  series  of  high  melting-point  waxes,  also  petro- 
latums of  extremely  high  quality,  and  new  types  of  asphalt  of  excel- 
lent ductility  and  penetration  relations.  The  same  is  true  to  a  cer- 
tain extent  with  other  light  hydrocarbons,  including  liquid  ethane, 
which  dissolves  much  less  oil  than  liquid  propane  and  throws  asphalt 
completely  out  of  solution.  A  mixture  of  methane  and  propane 
behaves  similarly  to  ethane.  Liquid  butane,  on  the  other  hand  is 
too  good  a  solvent  to  be  effective  in  removing  the  asphalt.  For 
the  complete  removal  of  wax,  asphalt,  heavy  ends,  naphthenic  com- 
pounds and  color  bodies,  liquid  propane  is  generally  more  efficient 
than  any  other  solvent  known  at  present 

Propane  gas,  by  simple  compression  and  liquefaction,  may  be 
converted  into  a  solvent  having  the  unique  properties  (under  proper 
conditions  of  temperature  and  pressure)  of  separating  each  of  the 
foregoing  undesirable  constituents.  It  owes  its  versatility  to  the 
fact  that  its  properties  change  rapidly  over  the  particular  tempera- 
ture range  between  —44°  and  +215°  F.  Over  this  range,  it 
possesses  the  properties  of  a  series  of  solvents,  any  one  of  which 
can  be  obtained  by  raising  or  lowering  the  temperature,  or  chang- 


VI  METHODS  OF  REFINING  127 

ing  the  pressure,  or  by  combining  these  two  operations.  Pure 
propane  boils  at  —  44°  F.  under  i  atmosphere  pressure,  exerts  a 
pressure  of  126  Ib.  per  sq.  in.  at  70°  F.,  and  has  a  critical  pressure 
of  643  Ib.  at  212.2°  F.  Over  this  range  propane  changes  from  a 
typical  liquid  to  a  fluid  possessing  substantially  the  properties  of  a 
gas.  Between  70°  and  —  44°  F.,  its  main  uses  are  in  connection 
with  dewaxing.  At  temperatures  above  70°  F.,  it  finds  its  use  as  a 
preferential  precipitant.  Thus,  in  the  range  of  100°  to  140°  F., 
asphalt  is  only  slightly  soluble  in  propane,  whereas  at  these  same 
temperatures  both  oil  and  wax  dissolve  completely.  Between  100° 
and  212°  F.  and  at  the  vapor  pressure  of  propane,  instead  of  be- 
having as  an  ordinary  liquid  and  dissolving  more  of  any  partially 
soluble  substances  as  the  temperature  is  raised,  it  actually  dissolves 
less.  The  heavier  and  more  naphthenic  compounds  are  thrown  out 
first,  but  as  the  properties  of  propane  become  increasingly  those  of 
gases,  it  dissolves  less  and  less  oil,  until  no  viscous  oil  remains  in 
solution  at  212.2°  F. — the  critical  temperature  of  propane.  This 
property  makes  it  possible  to  recover  by  simple  decantation  a  large 
proportion  of  the  propane  in  a  substantially  pure  state,  without 
the  necessity  to  vaporize  it  by  the  usual  method. 

To  utilize  these  varying  properties  of  propane  on  a  stock  con- 
taining all  the  foregoing  undesirable  constituents,  a  typical  cycle 
consists  in  mixing  the  oil  with  4  to  6  times  its  volume  of  liquid 
propane  at  120°  to  150°  F.,  which  will  throw  out  of  solution  prac- 
tically all  of  the  asphalt.  The  latter  may  be  settled  out  and  drawn 
off  as  a  liquid  because  it  contains  a  substantial  quantity  of  dissolved 
propane.  The  remaining  solution  can  then  be  rapidly  chilled  by 
the  simple  expedient  of  lowering  the  pressure  and  allowing  a  small 
quantity  of  the  propane  to  evaporate  until  a  temperature  of 

20°   to  — 40°    F.    is   attained,   whereupon   the   wax  will   be 

thrown  out  of  solution  and  may  be  removed  by  settling  or  prefer- 
ably by  filtration.  The  propane  solution  is  then  brought  back  to 
room  temperature,  and  may  either  be  treated  with  relatively  small 
quantities  of  sulfuric  acid  to  remove  the  color  bodies  and  naphthenic 
constituents,  or  else  be  heated  without  any  additions,  in  stepwise 
fashion,  to  about  200°  F.  Under  these  conditions  a  series  of  cuts 
of  varying  composition  is  separated  out;  the  first  is  composed  of 
very  heavy  ends,  resinous  constituents,  and  the  more  heavy  naph- 


128          METHODS  OF  MINING,  TRANSPORTING  AND  REFINING  VI 

thenic  constituents  of  the  oil,  and  each  cut  becomes  lighter  and 
more  paraffinic,  until  the  last  material  left  in  solution  is  a  rela- 
tively low-boiling,  highly  paraffinic,  light-colored  oil. 

The  term  upropane  de-asphalting"  is  usually  applied  to  those 
cases  where  the  heavy  product  is  a  mixture  containing  black,  pitchy 
material.  This  operation  may  include  removal  of  only  a  small 
amount  (approximately  3.5  per  cent)  of  high  melting-point  asphalt 
from  a  Mid-continental  crude,  to  a  much  larger  percentage  from  a 
California  crude.  In  the  latter  case,  the  separated  asphalt  had  a 
specific  gravity  at  60°  F.  of  1.031,  a  penetration  at  77°  F.  of  35, 
a  fusing-point  (R.  and  B.  method)  of  118°  F.,  and  over  99.6  per 
cent  soluble  in  CS2,  CC14  and  86°  petroleum  naphtha,  respectively. 

Attempts  have  also  been  made,  but  without  success,  to  utilize 
the  solvent  extraction  method  to  recover  the  bituminous  constitu- 
ents and  felt  respectively  from  the  waste  material  produced  in  the 
manufacture  of  asphalt  roofings  and  shingles.86  On  the  other  hand, 
it  has  given  satisfactory  results  in  recovering  montan  wax  from 
lignite  at  Thuringia,  Saxony,  and  from  pyropissite  at  Weissenfels, 
near  Halle,  Germany.  Benzol  is  generally  used  for  this  purpose, 
although  in  certain  cases  petroleum  distillates  have  given  good  re- 
sults. The  high  market  price  of  montan  wax  in  comparison  to 
asphalt  undoubtedly  accounts  for  this. 

METHODS  OF  STORAGE 

Bituminous  substances  which  are  capable  of  liquefying  under 
heat  are  usually  stored  in  metal  tanks  of  various  capacities.  These 
may  be  equipped  with  steam-coils.  One  device  consists  in  con- 
structing a  small  metal  tank  within  a  larger  one,  the  smaller  unit 
being  provided  writh  the  steam  coils  to  conserve  the  heat.87 


CHAPTER  VII 

MINERAL  WAXES 

OZOKERITE 

Ozokerite  is  a  native  mineral  wax,  composed  of  the  higher  mem- 
bers of  the  CnH2n+2,  and  CnH2n  series  of  hydrocarbons.  It  occurs 
in  deposits  usually  associated  with  petroleum.  Certain  varieties 
carry  a  proportion  of  petroleum  in  solution  with  the  wax,  and  the 
more  petroleum  present,  the  softer  will  be  the  consistency  and  lower 
the  fusing-point.  Ozokerite  as  ordinarily  found  is  fairly  hard,  and 
has  a  comparatively  high  fusing-point,  ranging  from  50  to  180°  F. 
The  fusing-point  has  been  recorded  as  high  as  200°  F.  (K.  and  S. 
method).  Ozokerite  containing  between  10  and  15  per  cent  of 
petroleum  in  solution,  shows  a  fusing-point  between  140  and  150°  F. 
The  petroleum  can  readily  be  evaporated  by  applying  a  moderate 
degree  of  heat,  and  is  expelled  during  the  refining  process. 

The  color  of  ozokerite  depends  upon  the  nature  and  extent  of 
the  impurities  present,  and  ranges  from  a  transparent  yellow  to  a 
dark  brown.  In  rare  instances,  ozokerite  occurs  in  a  dichroic  va- 
riety, showing  a  dark  green  color  by  reflected  light,  and  a  pure 
yellow  by  transmitted  light.  It  breaks  with  a  conchoidal  fracture, 
and  has  a  characteristic  waxy  lustre.  Its  streak  on  porcelain  varies 
from  a  transparent  white  to  a  pale  brown. 

Ozokerite  is  usually  found  filling  veins  or  fissures,  which  are 
very  irregular  in  structure,  varying  from  a  fraction  of  an  inch  to 
about  two  feet  in  thickness.  Some  extend  for  comparatively  long 
distances  whereas  others  pinch  out  very  suddenly.  The  veins  are 
usually  caused  by  faulting,  which  accounts  for  their  irregularity  and 
gives  the  vein  the  appearance  of  a  series  of  pockets.  The  indica- 
tions are  that  the  ozokerite  enters  the  faults  or  veins  from  below, 
which  is  borne  out  by  the  fact  that  the  material  mined  at  a  depth 
is  materially  softer  and  has  a  lower  fusing-point  than  that  obtained 
near  the  surface. 

Ozokerite  may  occur  in  a  pure  state  (comparatively  free  from 

129 


130  MINERAL  WAXES  VII 

mineral  matter),  which  proves  to  be  the  case  when  it  is  found  in 
vein  form,  or  it  may  be  associated  with  sandstone  or  shale.  In 
fact,  it  is  quite  common  for  the  entire  region  surrounding  the  vein 
to  be  saturated  with  ozokerite. 

A  paraffinaceous  petroleum  almost  invariably  occurs  in  the  strata 
underlying  the  ozokerite,  which  would  seem  to  indicate  that  the 
latter  must  have  been  produced  by  the  slow  hardening  and  probably 
also  the  oxidation  of  petroleum  throughout  centuries  of  time. 
Ozokerite,  itself,  however,  is  practically  free  from  oxygen.  In  this 
particular  case,  therefore,  the  effect  of  oxidation  is  to  eliminate 
hydrogen,  and  form  hydrocarbons  of  higher  molecular  weight. 

The  petroleum  underlying  the  ozokerite  usually  contains  from 
8  to  1 2  per  cent  of  paraffin,  which,  however,  is  entirely  different  in 
its  character  from  the  hydrocarbons  contained  in  the  ozokerite.1 
This  proves  conclusively  that  ozokerite  is  not  formed  merely  by  the 
evaporation  of  petroleum,  but  must  have  been  produced  by  a  process 
of  metamorphosis  or  polymerization. 

On  distilling  at  atmospheric  pressure,  ozokerite  decomposes, 
whereas  when  it  is  distilled  under  reduced  pressure,  its  composition 
changes  but  little.  Still  another  process  consists  in  distilling  the 
ozokerite  in  retorts  with  superheated  steam,  whereupon  the  residue 
in  the  retort  is  known  as  44ozokerite  pitch,"  which  when  combined 
with  rubber  has  been  marketed  under  the  name  "okonite." 

Ozokerite  as  it  is  mined  is  assorted  by  hand-picking  to  separate 
the  pure  material  from  that  associated  with  earthy  matter.  The 
latter,  which  is  known  as  "wax-stone,"  is  broken  up  to  remove  any 
lumps  of  rock  and  purified  by  extraction  with  boiling  water.  The 
method  used  for  this  purpose  is  very  crude,  and  consists  merely  in 
boiling  the  wax-stone  with  water  in  large  open  kettles.  The  sand- 
stone or  shale  separates  to  the  bottom  and  the  melted  ozokerite 
floats  in  a  layer  on  the  surface,  whereupon  it  is  skimmed  off,  boiled 
to  evaporate  the  water  and  cast  into  blocks.  The  commercial  ma- 
terial is  comparatively  free  from  mineral  matter,  rarely  containing 
over  2  per  cent. 

Ozokerite  may  be  refined  still  further  by  heating  to  120-200°  C., 
with  20  per  cent  by  weight  of  concentrated  sulfuric  acid,  or  with 
chromic  acid,2  or  by  treating  ozokerite  with  alkali  and  filtering  hot 
through  fuller's  earth,  animal  charcoal,  or  magnesium  silicate.  This 


VII  OZOKERITE  131 

bleaches  the  ozokerite,  forming  a  product  almost  white  in  color, 
known  as  "ceresine."  From  10  to  15  per  cent  of  the  ozokerite  is 
lost  during  the  treatment,  but  the  fusing-point  of  the  product  is 
increased.  The  final  traces  of  acid  are  removed  and  the  bleaching 
process  completed  by  adding  from  5  to  12  per  cent  of  dry  residue 
obtained  from  the  manufacture  of  "ferrocyanides."  The  main  dif- 
ferences between  ozokerite  and  ceresine  are  in  the  color  and 
fusing-point. 

Ozokerite  and  ceresine  are  used  in  the  manufacture  of  high- 
grade  candles,  colored  lead  pencils,  for  finishing  off  the  heels  and 
soles  of  shoes,  manufacturing  shoe  polishes,  electrical  insulating 
purposes,  as  an  acid-proof  coating  for  electrotypers*  plates,  and 
waxing  floors.  They  are  readily  soluble  in  turpentine,  petroleum 
distillates,  carbon  disulfide,  and  benzol,  by  scarcely  soluble  in  alcohol. 

Purified  ozokerite  and  ceresine  comply  with  the  following 
characteristics : 

(Test  i)*     Color  in  mass White  to  yellow  to  brown 

(Test  4)       Fracture Conchoidal 

(Test  5)       Lustre Dull  to  "waxy" 

(Test  6)       Streak Transparent  white  to  yellow 

(Test  7)       Specific  gravity  at  77°  F o. 85-1.00 

(Test  go)     Hardness,  Moh's  scale Less  than  i 

(Test  9^)     Penetration  at  32°  F o 

Penetration  at  77°  F 20-30 

Penetration  at  115°  F 150-250 

(Test  $c)     Consistometer  hardness  at    32°  F. . .  Above  100 

Consistometer  hardness  at    77°  F . .  .  20-40 

Consistometer  hardness  at  115°  F. .  .     5-15 

(Test    gd)  Susceptibility  factor Greater  than  80 

(Test  i$a)  Fusing-point  (K.  and  S.  method) 140-200°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method). . . .   155-225°  F. 

(Test  19)     Fixed  carbon K-IO    per  cent 

(Test  21)     Soluble  in  carbon  disulfide 95-100  per  cent 

Non-mineral  matter  insoluble * .     o-i      per  cent 

Mineral  matter 0-5      per  cent 

(Test  22)     Carbenes 0-3     per  cent 

(Test  23)     Non-mineral  matter  soluble  in  88° 

petroleum  naphtha 75~95    per  cent 

(Test  26)     Carbon 84-86    per  cent 

(Test  27)     Hydrogen. . .  <• 16-14    per  cent 

(Test  28)     Sulfur o-i .  5  per  cent 

(Test  29)     Nitrogen 0.0.5  per  cent 

(Test  30)     Oxygen 0-2     percent 

(Test  33)     Solid  paraffins 50-90    percent 

(Test  34^)  Sulfonation  residue 90-100  per  cent 

(Test  37*)   Saponifiable  constituents 0-2     per  cent 

*  The  numbers  refer  to  tests,  which  are  described  in  detail  in  Chapter  XXXII. 


132  MINERAL  WAXES  VII 

Very  often  ozokerite  and  ceresine  are  adulterated  with  paraffin 
wax,  rosin,  tallow,  stearic  acid  or  mineral  fillers  (such  as  talc,  kao- 
lin, gypsum,  etc. ) * 

Ozokerite  occurs  in  the  following  localities : 8 

EUROPE 

Poland  (Galicia).4  The  most  important  ozokerite  deposits  are 
found  in  the  Carpathian  Mountains  in  the  districts  of  Drohobycz 
(comprising  Boryslaw,  Wolanka  and  Truskawiec)  and  Stanislau 
(comprising  Dwiniacz,  Straunia,  Wolotkow  and  Niebylow).  It  is 
known  under  various  names,  e.g.,  "ozokerit,"  "fossil  or  montan 
wax,"  "mineral  fat,"  etc.  In  the  Moldau  region  it  is  called  "zietris- 
zit,"  and  around  the  Caspian  Sea,  "nephtgil,"  "neftgil,"  "naphatil," 
etc.  The  largest  deposit  is  located  as  Boryslaw,  a  small  town  in 
Galicia,  and  has  been  exploited  since  about  1859.  ^  'IS  found  at 
some  depths  below  the  surface,  associated  with  schist  and  sand- 
stone, and  it  is  mined  by  means  of  shafts  and  galleries.  About 
1500  shafts  have  been  sunk  in  the  district. 

The  following  varieties  of  ozokerite  are  recognized  in  the 
Boryslaw  district: 

(1)  Marble  wax,  found  100—200  m.  below  the  surface,  is  very 
hard,  of  a  pale  yellow  color,  with  greenish,  brownish  and  black 
markings,  giving  it  the  appearance  of  marble,  and  has  a  fusing- 
point  of  85  to  1 00°  C. 

(2)  Hard  wax  or  "crackwax"  (Sprungwax)  is  darker  in  color 
than  marble  wax,  shows  a  granular  fracture  and  a  fusing-point  of 
75  to  90°  C. 

(3)  Fibrous  wax,  or  "fibrewax,"  which  is  characterized  by  its 
fibrous  structure. 

(4)  Bagga  is  dark  in  color,  contains  clay,  and  has  a  compara- 
tively low  fusing-point  (40-60°  C.). 

(5)  Kindebal  or  "kinderball"  is  characterized  by  being  soft,  of 
low  fusing-point  (30-50°  C.)  and  a  black  color.     It  contains  pe- 
troleum and  mineral  matter. 

(6)  Blower  wax  ("blister  wax"  or  "matka")  is  a  pale  yellow, 
soft  variety,  which  is  squeezed  out  of  the  veins  due  to  the  presence 
of  the  surrounding  rocks. 

(7)  Lep  is  a  variety  of  ozokerite  associated  with  a  substantial 
proportion  of  mineral  matter. 

The  deposit  at  Wolanka  is  smaller  than  that  at  Boryslaw.    The 


VII  EUROPE  133 

occurrence  at  Truskawiec  differs  from  the  others  by  the  presence  of 
a  comparatively  large  percentage  of  sulfur.  The  ozokerite  in  this 
locality  is  associated  with  native  sulfur,  lead  sulfide,  gypsum,  and 
petroleum. 

At  Dwiniacz,  Straunia  and  Wolotkpw,  about  70  miles  south  of 
Boryslaw,  the  ozokerite  veins  are  located  some  distance  below  the 
surface,  in  beds  of  clay  between  layers  of  shale.  Considerable 
ozokerite  has  been  mined  in  this  district,  and  particularly  at 
Dwiniacz.  The  veins  vary  in  size  from  J4  *n-  to  about  I  ft.  The 
rock  in  the  vicinity  of  the  veins  is  impregnated  with  wax,  contain- 
ing an  average  of  2  per  cent. 

Rumania.  Deposits  of  ozokerite  are  also  found  in  a  spur  of  the 
Carpathian  Mountains  in  the  province  of  Moldavia  in  Rumania.  It 
has  been  mined  in  several  localities,  the  largest  vein  occurring  in  the 
city  of  Slanik,  beneath  a  bed  of  bituminous  shale,  associated  with  a 
vein  of  cannel  coal.  This  deposit  is  characterized  by  its  high  fusing- 
point,  in  the  neighborhood  of  200°  F.  (K.  and  S.  method). 

Russia.  Numerous  deposits  of  ozokerite  occur  throughout 
Russia,  including  specifically  the  following:5 

Terek  Province  (Northern  Caucasia}.  In  thq  vicinity  of  Gro- 
zny!, among  the  narrow  passes  along  the  road  from  Wozdwishensk 
and  Chatoi,  near  the  right  bank  of  the  Chanti-argun  River. 

Kuban  Province* (Northern  Caucasia] .  In  the  oil  fields  at  Mai- 
kop, near  Chadychenskaja,  on  so-called  Wax  Mountain,  about  5  km. 
from  Pshish  stream. 

Kutais  Province  (Transcaucasia}.  In  the  vicinity  of  Kutais,  2 
km.  east  of  the  village  Dznucisi,  between  the  rivers  Lechidary  and 
Merchery;  likewise  at  Achokrua  in  the  same  neighborhood;  also 
near  Charopan,  northeast  of  the  village  Tedeleti,  in  a  gorge  be- 
tween the  mountains  Gagberula  and  Syrch-Liberta. 

Tiflis  Province  (Transcaucasia}.  At  Sadzluri,  in  the  neighbor- 
hood of  Cori,  on  the  banks  of  Kran  River. 

Baku  Province  (Transcaucasia}.  In  the  Baku  oil  fields,  near 
the  town  Surachany,  also  on  the  Island  of  Suyatoi  in  the  Cas- 
pian Sea. 

Kars  Province  (Transcaucasia}.  In  the  region  of  Chala-Da- 
rasi,  in  the  vicinity  of  Kars.  Occurs  in  layers  containing  1.5  to  2.5 
per  cent  ozokerite  in  Uzbekistan,  at  Sel-rokho  and  Shorsu. 


134  MINERAL  WAXES  VII 

ASIA 

State  of  Turkestan.  On  the  Island  of  Cheleken  in  the  Caspian 
Sea;6  also  in  the  vicinity  of  Ferghana,  also  at  Neftedag  (Turkoman 
Republic)  in  veins  containing  50  to  80  per  cent  ozokerite,  termed 
locally  "lep." 

Siberia.    Along  the  eastern  shore  of  Lake  Baikal. 

Philippine  Islands.  On  the  Island  of  Leyete,  veins  of  ozokerite 
occur  at  the  contact  of  an  intrusive  dike  with  shales  and  sand- 
stones.7 

NORTH  AMERICA 

UNITED  STATES 

Utah.  The  most  important  deposit  occurs  near  Colton,  in 
Wasatch  County,  Utah,8*in  a  bed  of  oil  shale.  The  veins  extend 
from  about  2  miles  west  of  Colton  to  within  a  few  hundred  yards 
west  of  the  railroad  station  of  Soldier  Summit,  or  a  total  distance  of 
12  miles.  The  mineral  as  mined  contains  about  15  per  cent  ozo- 
kerite which  is  extracted  by  heating  the  crushed  ore  with  water  at 
60*70°  C,  whereupon  the  wax  floats  off.  A  peculiar  feature  of  this 
deposit  is  the  occurrence  of  fossil  shells  together  with  other  animal 
remains.  The  following  analytical  results  have  been  reported: 

(Test  i)       Color  in  mass Yellowish  brown 

(Test  4)       Fracture Conchoidal 

(Test  5)      Lustre Dull 

(Test  6)       Streak Pale  yellow 

(Test  7)       Specific  gravity  at  77°  F o. 899-0. 920 

(Test   9*)  Hardness,  Moh's  scale Less  than  i 

(Test    gb)   Penetration  at  77°  F 30 

Penetration  (100  g.,  15  sees.): 

at  20°  C 0.43  mm. 

at  30°  C 0.64  mm. 

at  40°  C i .  27  mm. 

at  50°  C 2.2    mm, 

at6o°C 3.8   mm. 

(Test  111)    Coefficient   of  expansion    between    10    and 

50°  C.,  per  deg.  C o.ooi 

(Test  I5/)    Fusjng-point 60  to  80°  C 

(Test  16)     Volatile,  212°  F.  I  hr o.o     per  cent 

Volatile,  325°  F.,  5  hrs 45.41    per  cent 

Volatile,  400°  F.,  5  hrs 65.2     per  cent 

(Test  19)     Fixed  carbon 9.6     per  cent 

(Test  21 )     Solubility  in  carbon  disulfide 99.46    per  cent 

Non-mineral  matter  insoluble o.  50    per  cent 

Free  mineral  matter 0.046  per  cent 


VII  NORTH  AMERICA  135 

(Test  12)     Carbcnes 2. 51    per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 81 .71    per  cent 

(Test  26)     Carbon 85.35    Per  cent 

(Test  27)    Hydrogen 13.86    per  cent 

(Test  28)     Sulfur 0.29    per  cent 

(Test  29)     Nitrogen 0.36    per  cent 

(Test  58)     Dielectric  strength  across  a  o.i-in.  gap over  30,000  volts 

Dielectric  constant 2 .03 

Power  factor o .  03 

Resistivity  across  a  i-cm.  cube 30  million  megohms 

Texas.  At  Thrall,  in  the  so-called  Thrall  Oil  Field,  another 
deposit  has  been  reported.9  The  crude  material  is  soft,  due  to  the 
petroleum  associated  with  it,  and  of  a  dark  brown  color.  It  has  a 
strong  odor  of  petroleum,  and  a  specific  gravity  at  77°  F.  of  0.875. 
On  being  heated  to  100°  C,  it  loses  14.72  per  cent,  and  at  180°  C. 
a  total  of  23. 1 4  per  cent  in  weight.  On  being  freed  from  petroleum, 
it  shows  a  fusing-point  of  175°  F. 

HATCHETTITE  OR  HATCHETTINE 

The  above  names  are  assigned  to  a  soft  variety  of  ozokerite 
fusing  in  the  neighborhood  of  120°  F.  (Test  I5/).  It  varies  in 
specific  gravity  from  0.90  to  0.98  at  77°  F.,  and  has  a  yellowish- 
white>  yellow  or  greenish-yellow  color.  It  was  named  after  C, 
Hatchett,  an  English  chemist  (1765-1847).  It  is  found  near 
Merthyr-Tydvil  in  Glamorganshire,  England,  also  at  Loch  Fyne  in 
Argylshire,  Scotland. 

SCHEERERITE 

A  native  wax  found  in  a  bed  of  lignite  near  St.  Gall,  Switzer- 
land. It  occurs  in  the  form  of  crystals  (monoclinic)  and  of  a  white, 
gray,  yellow,  green  or  pale  reddish  color.  It  is  more  or  less  trans- 
lucent to  transparent,  and  has  a  waxy  feel.  It  is  composed  chiefly 
of  the  members  of  the  paraffin  series,  and  fuses  at  a  temperature 
of  110-115°  F. 

KABAITE 

This  is  a  waxy  hydrocarbon  similar  to  ozokerite  or  scheererite, 
which  has  been  found  in  meteorites.  It  is  only  of  scientific  interest 
and  has  no  commercial  importance. 


136  MINERAL  WAXES  VII 

MONTAN  WAX 

As  stated  previously,  montan  wax  is  dissolved  from  certain  non- 
asphaltic  pyrobitumens  by  means  of  volatile  solvents,  such  as  benzol, 
xylol,  mixtures  of  benzol  with  methyl  alcohol  or  acetone,10  mixtures 
of  toluol  and  alcohol,11  etc.  By  extracting  under  pressure  the  yield 
is  materially  increased,  and  at  50  atmospheres  at  250-260°  C., 
benzol  will  extract  about  double  the  weight  than  at  I  atmosphere 
at  80°  C.12  The  lignite  or  pyropissite  is  first  dried,  then  granu- 
lated, and  finally  extracted.  The  extract  is  evaporated  to  recover 
most  of  the  solvent.  The  last  traces  of  solvent  are  expelled  from 
the  montan  wax  by  distillation  with  steam,  and  recondensed.  The 
crude  wax  differs  widely  according  to  the  source,  Thuringian  lignites 
yielding  a  hard  and  brittle  wax,  whereas  Bohemian  lignites  yield  a 
softer  product. 

Ninety  per  cent  of  the  montan  wax  present  in  the  lignite  is  re- 
moved in  this  manner.  About  10  to  15  per  cent  of  the  solvent  is 
lost,  but  the  high  price  obtainable  for  montan  wax  renders  this  per- 
missible. Usually  8  to  10  per  cent  of  montan  wax  is  extracted 
from  Thuringian  lignite  based  on  the  dry  weight  of  the  latter.  In 
exceptional  cases,  as  high  as  20  per  cent  has  been  obtained.  Pyro- 
pissite yields  between  50  and  70  per  cent  of  montan  wax  based  on 
its  dry  weight.  Unfortunately,  the  supply  of  pyropissite  is  largely 
exhausted. 

According  to  Edmund  Graefe,13  the  following  percentages  of 
montan  wax  are  extracted  by  benzol  from  the  dried  minerals  : 

Per  Cent 

Bohemian  Lignite i  •  29 

Texas  Lignite 2.07 

Lignite  from  the  region  of  the  Rhine 4-7° 

Lignite  from  Vladivostok 5-3& 

Lignite  from  Thuringia,  Saxony 9-°3 

Pyropissite 69. 50 

The  montan  wax  industry  is  not  practiced  in  the  United  States, 
but  is  localized  in  Saxony. 

Montan  wax  contains  esters  of  acids  possessing  high  molecular 
weight,  free  acids  and  a  small  quantity  of  substances  containing  sul- 
fur. Various  formulae  have  been  assigned  to  it,  including  CieH82O, 
CHO2  C20H58O  and  C^HgeO. 


VII  NORTH  AMERICA  137 

At  ordinary  temperatures  it  decomposes  when  distilled.    It  may, 
however,  be  purified  by  distilling  with  superheated  steam  in 
In  this  manner  the  following  products  are  obtained : 


(i 

(2 

(3 


Pure  odorless  montan  acid; 

Refined  montan  wax; 

A  bright  yellow  wax  containing  paraffin; 


(4)  A  residue  containing  paraffin; 

(5)  An  acid-free  pitch,15  known  as  "montanpitch"  or  "montan- 
wax  pitch,"  which  is  a  hard  waxy  material  having  a  dark  color. 

On  heating  with  glycerine,  an  ester  is  obtained  which  has  a 
much  higher  fusing-point  (in  the  neighborhood  of  200°  F.).  Mon- 
tan wax  may  be  blown  with  air,  either  alone  or  in  the  presence  of 
oxalic  acid,16  and  when  chlorinated  will  be  transformed  into  a  resi- 
nous product.17 

Commercial  montan  wax  complies  with  the  following  charac- 
teristics : 

(Test    i)     Color  in  mass; 

Crude  montan  wax Dark  brown 

Product  obtained   by  distillation   in 

vacuo Almost  white 

(Test   4)     Fracture Conchoidal 

(Test    5)     Lustre Waxy 

(Test    6)     Streak  on  porcelain Yellowish  brown  to  white 

(Test    7)     Specific  gravity  at  77°  F o. 90-1 .00 

(Test    9^)   Penetration  at  77°  F o  to  5 

(Test    9<r)   Hardness  at  77°  F.  (consistometer) Above  100 

(Test   $d)  Susceptibility  index >  100 

(Test  10)     Ductility  at  77°  F o.o 

(Test  I5/)    Fusing-point  (K.  and  S.  method) 170-200°  F. 

Note. — Montan  wax  obtained  from  pyropissite  has  a  higher  fusing-point  than 
that  obtained  from  lignite;  namely,  between  190  and  200°  F. 

(Test  17)     Flash-point 55°  to  575°  F. 

(Test  19)     Fixed  carbon 2-10  per  cent 

(Test  21)     Solubility  in  carbon  disulfide Greater  than  98  per  cent 

Non-mineral  matter  insoluble 0-2  per  cent 

Mineral  matter Less  than  2  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 80-100    percent 

(Test  26)     Carbon 82-83^  per  cent 

(Test  27)     Hydrogen *4~I4#  per  cent 

(Test  28)     Sulfur Less  than  i .  5  per  cent 

(Test  29)     Nitrogen Trace 

(Test3o)     Oxygen 3~6    percent 

(Test  33)     Solid  paraffins , o-io  per  cent 

(Test  34^)  Sulfonation  residue *. .     o-io  per  cent 

(Test  370)  Acid  value '. 28-33 

(Test  37*)   Ester  value 28-73 


138  MINERAL  WAXES  VII 

(Test  37<f)  Saponification  value 5°~95 

(Test  37<r)   Saponifiable  matter 50-80  per  cent 

Resins 20-30  per  cent 

Alcohols 5-20  per  cent 

Normal  wax  acids 49~5^K  per  cent 

Oxy-acids 3-5  per  cent 

Sulfur-containing  acids 6^-8  per  cent 

(characteristic  of  crude  montan  wax) 

(Test  38)     Asphaltic  constituents o  per  cent 

(Test  39)     Diazo  reaction No 

(Test  40)     Anthraquinone  reaction No 

Montan  wax  is  used  for  manufacturing  shoe  polishes,  phono- 
graphic records,  electrical  insulating  materials,  and  the  like,  also 
for  impregnating  timber  under  vacuum  followed  by  pressure.1 


18 


CHAPTER  VIII 

NATIVE  ASPHALTS  OCCURRING  IN  A  FAIRLY 
PURE  STATE 

Under  this  heading  will  be  considered  the  most  important  as- 
phalt deposits  containing  less  than  10  per  cent  of  mineral  matter 
figured  on  the  dry  weight.  These  include  exudations  or  seepages  of 
liquid  or  semi-liquid  asphalts,  also  surface  overflows  and  lakes. 
Most  of  these  are  characterized  by  being  liquid  to  semi-liquid  at 
normal  atmospheric  temperature,  and  by  containing  a  comparatively 
large  proportion  of  volatile  matter.  Only  a  few  of  these  deposits 
are  of  value  commercially. 

The  principal  deposits  are  as  follows : 

NORTH  AMERICA 

UNITED  STATES 
Kentucky. 

Breckinridge  County.  The  so-called  "Tar  Springs"  situated 
about  4  miles  south  of  Cloverport  on  Tar  Creek,  have  been  known 
for  many  years.  They  occur  as  seepages  of  pure,  soft  asphalt  at 
the  base  of  an  overhanging  cliff  of  sandstone  where  it  joins  a 
stratum  of  limestone.  The  asphalt  is  accompanied  by  water  charged 
with  sulfur  compounds,  and  the  surrounding  rocks  abound  in  ma- 
rine fossils. 

Gray  son  County.  Similar  seepages  abound  along  Big  Clifty 
Creek  and  its  tributaries,  in  the  vicinity  of  Grayson  Springs  station. 
Some  exude  from  sandstone  and  others  from  clay  or  shale.  The 
seepages  carry  between  5  and  10  per  cent  of  free  mineral  matter, 
the  balance  consisting  of  a  very  soft,  "stringy"  asphalt  containing  a 
large  proportion  of  volatile  ingredients  and  yielding  about  15  per 
cent  of  fixed  carbon. 

139 


140          NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

Oklahoma. 

There  are  only  a  few  minor  occurrences  of  pure  asphalt  found 
in  Oklahoma  in  the  form  of  seepages,  including  the  following: 

Carter  County.  NE  J4,  Sec.  10,  T  2  S,  R  2  W;  10  miles  north 
of  Wheeler. 

Murray  County.  SW  J4,  SE  ^4,  Sec.  15,  T  i  S,  R  3  E;  3 
miles  south  of  Sulphur. 

Neither  of  these  has  any  commercial  importance. 

Utah. 

Uinta  County.  A  pure,  solid  asphalt  is  found  in  Tabby  Can- 
yon, a  branch  of  the  Duchesne  River,  8  to  9  miles  south  and  west 
of  the  town  of  Theodore  and  about  30  miles  west  of  Ft.  Duchesne. 
It  has  been  exploited  under  the  name  "tabbyite"  *  and  tests  as 
follows  : 

(Test    4)     Fracture Conchoidal 

(Test    5)     Lustre Bright 

(Test    6)     Streak Black 

(Test    7)     Specific  gravity  at  77°  F i  .006-1 .010 

(Test    90)  Hardness,  Moh's  scale Less  than  i 

(Test    9^)   Penetration  at  77°  F o 

(Test    9<r)    Consistency  at  77°  F 80.0 

(Test  i$a)  Fusing-point  (K.  and  S.  method) 178°  F. 

(Test  1 6)     Volatile  matter,  325°  F.  in  5  hrs 2.78  per  cent 

Volatile  matter,  400°  F.  in  5  hrs 6.40  per  cent 

(Test  19)     Fixed  carbon 8 .08-  9 . 2  per  cent 

(Test  21 )     Soluble  in  carbon  disulfide 94.7  -92.  i  per  cent 

Non-mineral  matter  insoluble 0.5-1.1  per  cent 

Free  mineral  matter 4.8-6.8  per  cent 

(Test  22)     Carbenes o.o  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 61  per  cent 

(Test  25)     Carbon 82  per  cent 

(Test  26)     Hydrogen n  per  cent 

(Test  27)     Sulfur 2  per  cent 

(Test  28)     Nitrogen 2-2.5  per  cent 

Undetermined 2  per  cent 

Boxelder  County.  .A  pure  viscous  asphalt  deposit  occurs  below 
the  bed  of  Great  Salt  Lake,  about  10  miles  south  of  Rozel,  in  the 
Promontory  Range.2  It  is  found  in  a  series  of  horizontal  veins  3 
to  5  ft.  thick  interposed  between  beds  of  clay,  continuing  to  a  depth 
of  at  least  140  ft.  It  is  highly  probable  that  a  lake  of  asphalt 
occurred  at  this  point  centuries  ago,  which  in  time  became  covered 
with  sediments,  giving  rise  to  a  series  of  veins. 


VIII  NORTH  AMERICA  141 

At  the  present  time,  masses  of  asphalt  exude  through  the  uncon- 
solidated  material  at  the  bottom  of  the  lake,  and  float  to  the  sur- 
face in  lumps  i  to  2  ft.  in  diameter.  This  occurrence  corresponds 
very  closely  with  the  Dead  Sea  deposit.  On  analysis,  the  asphalt 
tests  as  follows: 

(Test    5)     Lustre Very  bright 

(Test    6)     Streak Black 

(Test    7)     Specific  gravity  at  77°  F 1 .02 

(Test   gb)  Penetration  at   32°  F.  (200  g.  in  60  sees.) 12 

Penetration  at    77°  F.  (100  g.  in    5  sees.) 50 

Penetration  at  115°  F.    (50  g.  in    5  sees.) 170 

(Test  loo)  Ductility  at  77°  F 70  cms. 

(Test  16)     Volatile  at  325°  F.  in  5  hrs 2.33  per  cent 

Volatile  at  325°  F.  in  7  hrs . . . .  3.4    per  cent 

(Test  19)     Fixed  carbon 4. 56  per  cent 

(Test  21 )     Soluble  in  carbon  disulfide 95 .00  per  cent 

Non-mineral  matter  insoluble i .  84  per  cent 

Free  mineral  matter 3.16  per  cent 

Note. — Has  unusually  high  adhesiveness,  ductility  and  cementing  qualities.  > 

California. 

Kern  County.  Deposits  of  asphalt  occur  in  the  so-called  "As- 
phalto  Region"  in  the  western  part  of  Kern  County,  about  50 
miles  west  of  Bakersfield,  in  the  form  of  large  springs;  also  as 
veins.  The  character  of  the  asphalt  varies  greatly,  both  in  consis- 
tency and  purity.  The  superficial  overflow  covers  an  area  of  7 
acres,  in  a  layer  2  to  4  ft.  thick  overlying  sand  and  clay.  Part  of  it 
has  hardened  on  account  of  exposure  to  the  elements,  and  other 
portions  are  still  soft  and  viscous.  A  vein  of  asphalt  also  occurs  in 
the  vicinity  of  the  overflow,  filling  a  fault,  varying  from  2  to  8  ft. 
in  width,  averaging  about  4  ft.  The  nature  of  the  asphalt  in  the 
vein  is  similar  to  that  of  the  overflow. 

The  asphalt  carries  from  3  to  30  per  cent  mineral  matter, 
mostly  sand  and  clay,  also  gas,  which  is  evidenced  by  the  fact  that 
it  loses  between  5  and  15  per  cent  in  weight  on  being  heated  to 
212°  F.  for  one  hour.  The  run  of  the  mine  averages  85  per  cent 
asphalt,  10  per  cent  mineral  matter  and  5  per  cent  moisture  and 
gas.  It  is  refined  by  heating,  which  drives  off  the  water  and  gas 
and  permits  a  certain  amount  of  the  mineral  matter  to  settle  out. 
According  to  Clifford  Richardson8  the  refined  asphalt  tests  as 
follows : 


142          NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

(Test    4)     Fracture Semi-conchoidal 

(Test    5)     Lustre Bright  to  dull 

(Test    6)     Streak Black 

(Test    7)     Specific  gravity  at  77°  F i  .06 

(Test    9^)   Penetration  at  77°  F 0-27 

(Test  1 6)     Volatile  matter,  325°  F.,  5  hrs 6.6  per  cent 

Volatile  matter,  400°  F.,  5  hrs 19.9  per  cent 

(Test  19)     Fixed  carbon 8.0  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 89.8  per  cent 

Non-mineral  matter  insoluble 3.4  per  cent 

Free  mineral  matter 6.8  per  cent 

Total 100.0  per  cent 

(Test  22)     Carbenes 0.3  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 53 .4  per  cent 

(Test  340)  Saturated  hydrocarbons 28 .6  per  cent 

The  asphalt  resembles  gilsonite  in  its  outward  appearance,  but 
is  considerably  softer,  yielding  a  smaller  percentage  of  fixed  carbon. 
Richardson  infers  that  the  asphalt  has  been  metamorphized  only 
part  way  to  gilsonite.  This  deposit  of  asphalt  is  not  being  worked 
at  the  present  time,  but  is  of  interest  from  the  scientific  viewpoint. 

A  sample  of  liquid  asphalt  taken  from  seepages  in  the  so-called 
"McKittrick  Region,"  in  Kern  County,  shows  specific  gravity  at 
77°  F.  of  0.99,  and  16  per  cent  loss  on  being  heated  to  400°  F.  for 
seven  hours.  In  its  original  state  it  is  very  soft  and  sticky. 

San  Luis  Obispo  County.  A  large  surface  deposit  of  soft  asphalt 
produced  by  seepage  from  the  surrounding  shale  occurs  at  Tar 
Spring  Creek,  a  tributary  of  the  Arroyo  Grande,  20  miles  southeast 
of  San  Luis  Obispo,  covering  an  area  of  200  ft.  in  diameter  and 
3-15  ft.  deep.  As  it  exudes  from  the  shale,  the  asphalt  is  soft  and 
accompanied  with  sulfurous  water;  near  the  edge  of  the  deposit  it 
appears  quite  hard,  and  at  the  edge  it  verges  towards  brittleness. 
No  analytical  results  are  available. 

Santa  Barbara  County.  Veins  of  high-grade  asphalt  occur  in 
La  Graciosa  hills  about  4  to  5  miles  east  of  the  town  of  Graciosa  in 
the  so-called  Santa  Maria  Region.  These  are  irregular  in  forma- 
tion, extending  through  shale  and  sandstone,  and  varying  from 
several  inches  to  2  ft.  in  width.  Associated  with  these  veins  are  beds 
of  impregnated  asphaltic  shale,  extending  over  an  area  of  a  mile  or 
two,  and  containing  a  variable  percentage  of  asphalt.  One  of  the 
striking  features  of  these  Recurrences  is  the  presence  of  marine 
fossils  in  the  veins  and  surrounding  shale,  indicating  that  the  asphalt 
is  of  animal  origin^ 


VIII  NORTH  AMERICA  143 

Oregon. 

Coos  County.  An  unusual  type  of  asphalt  occurring  in  beds  of 
coal  has  been  reported  at  the  old  Newport  Mine  at  Libby,  and  old 
Ferrey's  Mine  at  Riverton,  in  the  Coos  Bay  coal  field.  It  is  hard 
and  brittle,  and  similar  to  coal  in  appearance.  About  one-third  of 
the  non-mineral  matter  is  insoluble  in  carbon  disulfide,  yet  the  ma- 
terial fuses  as  a  comparatively  low  temperature  (about  300°  F.), 
and  has  a  specific  gravity  of  less  than  i.io  at  77°  F.  It  may  be  re- 
garded as  a  metamorphized  asphalt  or  a  glance  pitch.  It  consti- 
tutes one  of  those  substances  encountered  occasionally,  falling  on  the 
border  line,  so  that  it  becomes  a  difficult  matter  to  arrive  at  its  cor- 
rect classification.  For  a  long  time  it  was  known  as  a  "Pitch 
Coal."  4  The  following  data  would  seem  to  indicate  that  it  par- 
takes of  the  properties  of  an  asphalt  rather  than  of  a  glance  pitch: 

(Test    4)  Fracture Hackly  to  conchoidal 

(Test    5)  Lustre Fairly  dull  to  brilliant 

(Test    6)  Streak Black 

(Test    7)  Specific  gravity  at  77°  F 1 .09  to  i .  28 

(Test    9*)  Hardness,  Moh's  Scale About  I 

(Test    9^)  Penetration  at  77°  F o 

(Test    9f)  Consistency  at  77°  F Above  100 

(Test  14^)  In  flame Softens  and  flows 

(Test  i$a)  Fusing-point  (K.  and  S.  method) 302  to  330°  F. 

(Test  16)  Volatile  at  325°  F.,  5  hrs o.  5  per  cent 

(Test  19)  Fixed  carbon 10-13  per  cent 

(Test  21)  Soluble  in  carbon  disulfide 100  per  cent 

(Test  22)  Carbenes o  per  cent 

(Test  23)  Soluble  in  88°  petroleum  naphtha About  10  per  cent 

(Test  27)  Sulfur o.  5-1  .o  per  cent 

MEXICO 
State  of  Tamaulipas. 

Asphalt  springs  occur  at  numerous  points  along  the  Tamesi 
River,  which,  according  to  Clifford  Richardson,5  show  the  follow- 
ing characteristics : 

(Test    7)     Specific  gravity  at  77°  F i  .04-1 . 12 

(Test   9*)   Penetration  at  77°  F 40-16 

(Test  16)     Loss  at  212°  F.  until  dry 10-20         per  cent 

Loss  at  325°  F.  for  5  hrs.  (refined  material). . .     i .  5-4. 8    per  cent 

Loss  at  400°  F.  for  5  hrs 4.3-8.9     per  cent 

(Test  17)     Flash-point 308°  F. 

(Test  19)     Fixed  carbon 12.6-16.  i  per  cent 

(Test  21)     Solubility  in  carbon  disulfide  (refined  material).   89. 0-99 . o  per  cent 

Non-mineral  matter  insoluble o.  5-  i .  8  per  cent 

Free  mineral  matter 0.5-9.1  per  cent 


144          NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

Other  deposits  in  the  neighborhood  show  a  larger  proportion  of 
mineral  matter,  often  running  as  high  as  33  per  cent 

Chijol.  Asphalt  springs  occur  also  near  Chijol,  25  miles  west 
of  Tampico.  They  are  comparatively  soft  in  consistency,  testing 
over  90  per  cent  soluble  in  carbon  disulfide,  with  less  than  10  per 
cent  mineral  matter, 

State  of  Vera  Cruz. 

District  of  Tuxpan.  Similar  deposits  are  found  in  the  neigh- 
borhood of  Tuxpan,  some  distance  from  the  Tuxpan  River,  having 
the  same  general  characteristics  as  the  preceding.  Analyses  show 
that  90  per  cent  is  soluble  in  carbon  disulfide,  with  less  than  10  per 
cent  of  mineral  matter. 

District  of  Chapapote.  Similar  deposits  are  found  15  miles 
from  Timberdar  at  the  head  of  the  Tuxpan  River,  of  an  exceed- 
ingly pure  character,  testing  99  per  cent  soluble  in  carbon  disulfide, 
and  less  than  i  per  cent  mineral  matter.  The  asphalt  varies  in 
consistency  from  a  semi-liquid  to  a  comparatively  hard  solid,  de- 
pending upon  the  length  of  time  it  has  been  exposed  to  the  weather.6 

In  the  early  days,  the  name  "chapapote"  was  applied  generally 
to  designate  viscous,  semi-liquid  asphalts  corresponding  in  charac- 
teristics to  the  type  of  asphalt  found  in  this  district 

CUBA 

Province  of  Matanzas.  A  pit  filled  with  pure  liquid  asphalt 
has  been  reported  in  the  neighborhood  of  Santa  Catalina.  This 
occurs  in  a  bed  of  serpentine,  and  originally  produced  in  the  neigh- 
borhood of  20  barrels  of  semi-liquid  asphalt  a  day,  derived  pre- 
sumably from  underlying  petroleum-bearing  strata.  Other  pits  in 
the  neighborhood  similarly  yield  liquid  asphalt 

Liquid  asphalt  is  also  found  near  Cardenas  and  extends  some 
distance  eastwards.  Another  deposit,  known  as  "Dos  Companeros 
Mine,"  occurs  in  the  Guametos  District,  near  Sabanilla  de  la  Palma, 
testing  as  follows : 

(Test    7)    Specific  gravity  at  77°  F 1.05-1.06 

(Test  16)    Volatile  at  220°  F 2-18  per  cent 

Volatile  at  325°  F.,  5  hrs 2.8-6.8  per  cent 


VIII  NORTH  AMERICA  145 

(Test  19)    Fixed  carbon 10-12   per  cent 

(Test  21)    Soluble  in  carbon  disulfide 98-99    per  cent 

Non-mineral  matter  insoluble o-i .  5  per  cent 

Mineral  matter 0.5-2.0  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha 73-77   per  cent 

Another  deposit  occurs  7  miles  south  of  Hato  Nuevo,  testing 
similar  to  the  preceding.  All  of  these  deposits  contain  more  or 
less  adventitious  water. 

Province  of  Santa  Clara.  A  variety  of  hard  asphalt,  ap- 
proaching glance  pitch,  is  found  in  Calabazar  District,  near  the 
town  of  Mata,  in  a  mine  known  as  "El  Provenir."  It  tests  as 
follows : 7 

(Test    i)     Color  in  mass Black 

(Test    4)     Fracture Conchoidal 

(Test    5)    Lustre Bright 

(Test    6)    Streak  on  porcelain Brownish  black 

(Test    7)     Specific  gravity  at  77°  F i  .09-1 .11 

(Test  19)    Fixed  carbon 18 .o-  19.2  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 97 . 5-  97 . 6  per  cent 

Non-mineral  matter  insoluble 0.5-    0.9  per  cent 

Mineral  matter 2.0-    i . 5  per  cent 


Total '. 100.0-100.0  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 39. 4-  57.4  per  cent 

Province  of  Camaguey.  Deposits  of  pure  soft  asphalt  occur 
near  the  village  of  Minas,  about  30  miles  from  Nuevitas  and  20 
miles  from  Puerto  Principe  City.  The  asphalt  is  associated  with 
water,  and  tests  as  follows: 

(Test   7)    Specific  gravity  at  77°  F.  (dry) , i  .079 

(Test    gb)  Hardness  at  77°  F.  (dry) 35 

(Test  16)    Volatile  at  325°  F.  in  5  hrs 6.2  per  cent 

Penetration  of  residue  at  77°  F 12 

(Test  21)    Soluble  in  carbon  disulfide 94-  5  per  cent 

Non-mineral  matter  insoluble 0.3  per  cent 

Mineral  matter 5.2  per  cent 

Total 100. o  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha 70.0  per  cent 


Province  of  Santiago  de  Cuba*    A  small  deposit  of  soft  as- 
phalt has  been  reported  in  Victoria  de  las  Tunas  District,  $l/2  miles 


146  NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

southwest  of  San  Manuel,  in  a  mine  known  as  "Punta  la  Brea," 
which  tests  as  follows : 

(Test    7)     Specific  gravity  at  77°  F o.  990 

(Test  16)     Volatile  at  325°  F.  in  5  hrs 6.3  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 99. 1  per  cent 

Non-mineral  matter  insoluble 0.5  per  cent 

Mineral  matter 0.4  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha 88 . 8  per  cent 


SOUTH  AMERICA 

VENEZUELA 

State  of  Bermudez.  The  so-called  Bermudez  "Pitch  Lake"  8 
is  situated  near  the  town  of  Guanoco  in  the  District  of  Benitez,  3 
miles  above  the  confluence  of  the  San  Juan  and  Guanoco  Rivers,  25 
miles  west  of  the  Gulf  of  Paria,  and  105  miles  due  west  of  Trinidad 
Lake.  It  is  covered  with  vegetation  and  water  in  pools.  A  typical 
view  is  shown  in  Fig.  43.  The  lake  represents  the  exudation  of  soft 
asphalt  from  springs  distributed  at  different  points  over  its  area,  and 
constitutes  one  of  the  largest  deposits  of  pure  asphalt  yet  discov- 
ered, extending  over  mo  acres  and  varying  in  depth  from  2  to 
20  ft,  averaging  5  ft. 

Its  consistency  varies  in  different  parts  of  the  lake.  Where  it 
exudes  from  the  springs,  it  is  quite  soft,  and  disengages  gas  freely 
and  copiously.  The  surface  of  the  deposit  hardens  slowly  on  expo- 
sure to  the  weather,  forming  a  crust  varying  from  several  inches  to 
several  feet  in  thickness,  and  sufficiently  firm  to  support  the  weight 
of  a  man.  The  asphalt  underneath,  however,  is  still  soft  and  semi- 
liquid,  and  there  are  numerous  breaks  through  the  surface  from 
which  the  soft  asphalt  oozes.  At  the  edge  of  the  lake  the  asphalt 
is  hard  and  brittle,  due  to  the  evaporation  of  the  volatile  constitu- 
ents by  the  heat  of  the  sun.  Certain  portions  of  the  lake  have  been 
converted  into  a  cokey  mass  as  a  result  of  fires  which  must  have 
swept  over  the  lake  years  ago,  due  probably  to  the  combustion  of 
vegetation  growing  profusely  at  the  edges. 

To  remove  the  asphalt,  a  dam  is  built  of  slag  and  waste  and 


VIII 


SOUTH  AMERICA 


147 


Courtesy  of  Barber  Co. 


FIG.  43. — -View  of  Bermudez  Asphalt  Lake. 


Courtesy  of  Barber  Co. 
FlG.  44. — Transporting  Bermudez  Asphalt. 


148          NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

the  water  pumped  out  The  asphalt  is  then  dug  out  by  hand  and 
loaded  into  small  cars,  which  are  hauled  by  cable  to  a  railroad  run- 
ning to  Guanoco,  8  miles  distant,  where  it  is  either  refined  or  run 
directly  to  a  loading  jetty,  whence  it  is  transferred  to  steamers  as 
shown  in  Fig.  44, 

The  crude  asphalt  has  the  following  composition : 9 

(Test  21)  Soluble  in  carbon  disulfide 64.39  per  cent 

Non-mineral  matter  insoluble 3 . 53  per  cent 

Mineral  matter 2 .08  per  cent 

(Test  25)    Water 30.00  per  cent 


Total 100.00  per  cent 

According  to  Clifford  Richardson,10  the  dried  crude  Bermudez 
asphalt  has  the  following  composition : 

(Test    i)    Color  in  mass Black 

(Test   4)    Fracture Conchoidal 

(Test    5)    Lustre Bright 

(Test   7)    Specific  gravity  at  77°  F i  .05-1 .075 

(Test  16)    Volatile  at  400°  F.  in  5  hrs.  (dried  material). .  5.81-16.05  per  cent 

(Test  21 )     Soluble  in  carbon  disulfide 90-98    per  cent 

Non-mineral  matter  insoluble o .  62-6 . 45  per  cent 

Free  mirteral  matter o.  50-3 . 65  per  cent 

The  crude  Bermudez  asphalt  is  melted  to  drive  off  the  moisture 
and  gas.  The  water  which  is  present  is  derived  from  the  heavy 
rains  and  by  overflows  from  the  surrounding  country.  It  is  not 
emulsified  with  the  asphalt  as  is  the  case  with  the  Trinidad  deposit. 
The  percentage  of  water  varies  from  10  to  about  40  per  cent  as  a 
maximum. 

Refined  Bermudez  asphalt  tests  as  follows:11 

(Test   4)    Fracture ; Conchoidal 

(Test   5)    Lustre Very  bright 

(Test   6)    Streak Black 

(Test   7)    Specific  gravity  at  77°  F i  .06-1 .085 

(Test   ga)  Hardness  on  Moh's  scale Less  than  i 

(Test   9^)  Penetration  at  1 15°  F 60 

Penetration  at  77°  F 20-30 

Penetration  at  32°  F 3 

(Test   9*)  Consistency  at  115°  F ,  7.7 

Consistency  at  77°  F •. 22. 7 

Consistency  at  32°  F 93. 8 

(Test   9<J)  Susceptibility  index 62. 5 


VIII  SOUTH  AMERICA  149 


(Test  io£)  Ductility  at  115°  F  .......................  14.5 

Ductility  at  77°  F  ........................   u 

Ductility  at  32°  F  ........................  o 

(Test  n)    Tensile  strength  at  115°  F  .................  0.60 

Tensile  strength  at  77°  F  ..................  3.45 

Tensile  strength  at  32°  F  ..................   10,  5 

(Test  15*)  Fusing-point  (K.  and  S.  method)  ...........   130-140°  F. 

(Test  15*)  Fusing-point  (R.  and  B.  method)  ...........   145-160°  F. 

(Test  16)    Volatile  matter,  325°  F.,  5  hrs  ..............  3.0-  6.0  per  cent 

Volatile  matter,  500°  F.,  5  hrs  ..............  8  .0-10.0  per  cent 

(Test  19)     Fixed  carbon  .............................  12.9-14.0  per  cent 

(Test  21)     Solubility  in  carbon  disulfide  ...............     92-97  per  cent 

Non-mineral  matter  insoluble  ..............   i  .  5-4.0  per  cent 

Free  mineral  matter  ......................   i  .  5-6.  5  per  cent 

(Test  22)    Carbenes  ____  .  ...........................  o.o-i  .o  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha  ........     60-75  per  cent 

(Test  26)     Carbon  .................................     82.88  per  cent 

(Test  27)    Hydrogen  ...............................     10.79  per  cent 

(Test  28)     Sulfur  ...................................       5.87  per  cent 

(Test  29)    Nitrogen  ................................      0.75  per  cent 

Total  ...............................  100.  29  per  cent 

(Test  33)     Solid  paraffins  ...........................  Trace 

(Test  340)  Saturated  hydrocarbons  ...................  23-25  per  cent 

(Test  yjd)  Saponification  value  ......................  28  .  o  per  cent 

(Test  380)  Free  asphaltous  acids  .....................  3.  5  per  cent 

(Test  38^)  Asphaltous  anhydrides  ....................  2.0  per  cent 

(Test  38^)  Asphaltenes  ..............................  35-3  per  cent 

(Test  38^)  Asphaltic  resins  ..........................  14.4  per  cent 

(Test  38*)  Oily  constituents  .........................  39.6  per  cent 

La  Brea  Deposit.  This  also  occurs  as  an  overflow  in  the  form 
of  a  lake  at  La  Brea,  in  the  Pedernales  oil  field,  on  the  northwest 
coast  of  the  Island  of  Capure,  in  the  delta  of  the  Orinoco  River, 
some  distance  east  of  the  Bermudez  Lake.  It  is  about  3200  ft. 
long  and  100  to  200  yards  wide,  and  is  fed  by  several  springs  and 
one  asphalt  cone.  Similar  deposits  on  a  smaller  scale  are  found  on 
the  neighboring  islands  of  Paquero  and  Del  Plata,  likewise  in  the 
District  of  Sucre,  where  cones  of  asphalt  occur  5  ft  high  and  30 
ft.  wide. 

State  of  Zulia. 

Maracaibo  Deposit.  A  number  of  asphalt  deposits  occur  in  the 
Inciarte  region,  in  the  District  of  Mara,  south  of  the  Limon  River, 
60  miles  west  of  the  city  of  Maracaibo.  Others  occur  at  La  Paz, 
a  short  distance  to  the  east  These  are  in  the  form  of  overflows, 
exuding  from  springs.  More  than  100,000  tons  were  collected 


150          NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

during  1901—1905,  but  operations  have  since  largely  ceased.  The 
asphalt  was  gathered  by  means  of  picks  and  shovels  and  trans- 
ported in  barges  down  the  Limon  River  to  the  island  Toas  at  the 
head  of  the  Gulf  of  Maracaibo,  where  it  was  loaded  on  board 
steamers.  It  melts  at  a  higher  temperature  than  the  Bermudez 
asphalt,  and  possesses  a  very  strong  and  characteristic  sulfurous 
odor. 

According  to  Clifford  Richardson  12  it  tests  as  follows : 

(Test    4)     Fracture Conchoidal 

(Test    5)    Lustre Very  bright 

(Test    6)     Streak Black 

(Test    7)     Specific  gravity  at  77°  F i  .06-1 .08 

(Test  90 )     Hardness,  Moh's  scale Less  than  i 

(Test  9^)     Penetration  at  77°  F.  ...  v 20-30 

(Test  16)     Volatile  at  325°  F.,  5  hrs i .  5-6  per  cent 

Volatile  at  500°  F.,  5  hrs 4.7-6.0  per  cent 

(Test  19)     Fixed  carbon 15.0-19.0  per  cent 

(Test  21)     Solubility  in  carbon  disulfide 92~97  per  cent 

Non-mineral  matter  insoluble 1.4-5.0  per  cent 

Free  mineral  matter i .  5-6 .  o  per  cent 

(Test  22)     Carbenes 1.5  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha 45~55  per  cent 

(Test  34)     Saturated  hydrocarbons 25-30  per  cent 


EUROPE 

FRANCE 

Department  of  Puy-de-D6me  (Auvergne).  In  the  vicinity  of 
Clermont-Ferrand,  seepages  of  soft  asphalt  exude  from  crevices 
in  the  rock,  containing  90  per  cent  of  asphalt,  7  per  cent  water,  and 
3  per  cent  mineral  substances.  The  exudations  are  comparatively 
small  in  amount,  and  the  asphalt  has  never  proved  of  importance 
commercially. 

At  Pont-du-Chateau  there  occur  extensive  deposits  of  rock  as- 
phalt, from  which  soft  asphalt  seeps  in  moderately  large  quantities 
and  is  caught  in  subsidiary  workings  excavated  for  this  purpose. 
Prior  to  1914,  approximately  100  tons  of  pure  liquid  asphalt  were 
recovered  annually  in  this  manner.  This  represents  practically  the 
only  locality  in  Europe  where  an  appreciable  quantity  of  pure  as- 
phalt is  obtained  at  the  mines. 


VIII  EUROPE  151 

ALBANIA 

Selenitza  (Sclinitza).  At  the  junction  of  the  Vojutza  (Vo- 
jusa)  and  Sauchista  Rivers,  extending  from  the  towns  of  Kanina 
to  Berat,  in  the  vicinity  of  the  Bay  of  Avlona  (Valona),  there 
occurs  a  fairly  large  deposit  of  moderately  hard  asphalt  in  sand- 
stone and  conglomerate,  in  veins  £s  wide  as  10  ft.  Marine  fos- 
sils are  associated  with  this  deposit,  indicating  it  to  be  of  animal 
origin.  The  asphalt  breaks  with  a  conchoidal  fracture,  showing  a 
high  lustre.  It  contains  between  8  and  14  per  cent  of  mineral  mat- 
ter, averaging  about  10  per  cent.  Comparatively  large  quantities 
have  been  mined  during  many  centuries. 

GREECE 

Zante.  An  extensive  deposit  of  asphalt  occurs  in  the  southern 
portion  of  the  Island  of  Zante,  in  the  form  of  springs  and  seepages. 
The  asphalt  is  very  soft  in  consistency,  having  a  specific  gravity  of 
i.oo  to  i. 02  at  77°  F.,  and  carrying  but  a  trace  of  mineral  matter, 
with  a  fairly  large  proportion  of  water  in  emulsion.  The  springs 
occur  in  a  region  of  clay  and  limestone,  more  or  less  saturated  with 
petroleum.  These  deposits  have  been  worked  for  many  generations. 
The  asphalt  is  refined  in  a  crude  way  by  the  natives  who  use  it  for 
calking  the  seams  of  ships,  and  as  a  mortar  for  cementing  together 
the  stones  of  buildings,  following  the  same  method  as  practiced 
centuries  ago. 

RUSSIA  1S 

Kutais  Province  (Transcaucasia).  In  the  neighborhood  of 
Osurgeti,  about  3  km.  north  of  the  railroad  station  Notanebi  and 
about  400  m.  from  the  railway  (near  the  villages  Yakobi  and  Na- 
rudcha),  there  occurs  a  vein  of  fairly  pure  asphalt  containing  9.66 
per  cent  ash.  Similarly,  at  Sakuprisgale  brook,  near  the  village  of 
Sameho,  about  4  km.  from  the  railroad  station  Notanebi,  there  is 
found  a  deposit  of  pure  hard  asphalt  containing  4.98  per  cent  ash. 

Tiflis  Province  (Transcaucasia).  In  the  vicinity  of  Tiflis,  on 
the  right  bank  of  the  Yora  River,  southwest  of  the  Cloister  of  Holy 
David  of  Garedchi,  there  occurs  a  deposit  of  hard  asphalt  contain- 
ing 3.86  per  cent  ash. 


152          NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

Uralsk  Province  (Russia  in  Asia).  In  the  so-called  Kirgisen 
Steppes,  near  where  the  rivers  Emba  and  Sagis  empty  into  the  Cas- 
pian Sea,  there  occur  asphalt  deposits  at  Imankara  and  Karamurat; 
also  about  4  km.  east  of  Alascha-Kasgen  there  are  found  two  de- 
posits of  pure  asphalt,  one  covering  4300  sq.  m.  and  the  other 
1600  sq.  m.,  ranging  from  a  hard  to  a  softer  material  of  elastic 
consistency. 

ASIA 

SYRIA  (LEVANT  STATES) 

Villayet  of  Beirut.14  At  Jebel  Keferie  (Kfarieh),  a  hill  near  the 
bend  of  the  Nahr  el  Kebir,  about  40  km.  from  the  sea,  on  the  road 
between  Latakia  and  Aleppo,  there  occurs  a  large  deposit  of  asphalt, 
covering  an  area  1400  by  1500  m.,  part  of  which  runs  quite  free 
from  mineral  contamination  (contains  as  low  as  y2  per  cent  ash). 
It  has  not  been  worked  to  any  extent,  on  account  of  the  difficulty  in 
transportation  to  the  coast 

MESOPOTAMIA  (IRAQ) 

Deposits  of  pure  asphalt  have  been  reported  at  the  following 
places : 

Hit.  Containing  64  per  cent  asphalt  and  36  per  cent  water. 
The  extracted  asphalt  contained  0.5  per  cent  ash  and  8.3  sulfur, 
fusing-point  (R.  and  B.)  47.5°  C.,  penetration  at  77°  F.  108. 

Ain  el  Maraj  (near  Kerkuk).  Containing  79  per  cent  asphalt 
and  21  per  cent  water.  The  extracted  asphalt  contained  3.8  per 
cent  ash  and  8.8  per  cent  sulfur,  fusing-point  (R.  and  B.)  64°  C., 
penetration  at  77°  F.  25. 

Ain  Ma9  Moura  (Ain  Mamurah).  Containing  72  per  cent  as- 
phalt and  28  per  cent  water.  The  extracted  asphalt  contained  0.7 
per  cent  ash  and  8.5  per  cent  sulfur,  fusing-point  (R.  and  B.) 
52.5°  C.,  penetration  at  77°  F.  73. 

Quijarah,  Ramadi  and  Abu  Gir.  Minor  asphalt  seepages  have 
been  noted. 

ASIATIC  RUSSIA 
Sakhalin. 

Province  of  Nutowo.  An  asphalt  lake,  known  as  the  "Great 
Okha  Asphalt  Lake,"  occurs  in  Okha,  on  the  east  coast  of  the  Island 
of  Sakhalin  in  a  swampy  valley,  associated  with  a  very  thick  variety 


VIII  ASIA  153 

of  petroleum,  exuding  in  the  neighborhood.  Where  the  asphalt 
emanates  from  the  springs,  it  is  very  soft  and  sticky,  but  towards 
the  edges  of  the  lake  it  is  hard  and  brittle.  The  asphalt  has  a 
rather  strong  odor,  and  contains  a  substantial  quantity  of  volatile 
matter.  As  mined,  it  contains:  asphalt  89.7  per  cent,  ash  1.18  per 
cent  and  water  9.03  per  cent,  and  has  a  fusing-point  of  73°  C.  (K. 
and  S.)  and  a  penetration  at  77°  F.  of  17.  This  asphalt  occupies 
an  intermediate  position  between  Trinidad  and  Bermudez  Lake  as- 
phalts.15 After  being  air-dried,  it  carries  0.75  per  cent  of  mois- 
ture, 0.22  per  cent  of  ash,  and  the  balance  pure  asphalt  containing 
0.80  to  0.85  per  cent  sulfur.  It  is  estimated  that  at  least  400,000 
tons  of  asphalt,  averaging  0.9  per  cent  of  mineral  matter,  are  pres- 
ent in  the  lake.  Up  to  the  present,  the  deposit  has  not  been  devel- 
oped commercially.16 

PHILIPPINE  ISLANDS 
Island  of  Leyte. 

Several  asphalt  deposits  have  been  found  in  this  region,  one 
near  the  head  of  the  Butason  River,  about  6  miles  from  the  Barrio 
of  Campocpoc,  on  the  northwestern  coast  of  the  island,  and  another 
near  the  town  of  Villaba.17  These  occur  in  limestone  and  sand- 
stone, and  extend  over  an  area  12  miles  long.  Outcrops  of  various 
grades  of  asphalt  have  been  reported,  including  the  solid,  viscous 
and  liquid  types.  Both  pure  and  rock  asphalts  are  found,  the  latter 
carrying  a  variable  proportion  of  sand.  Two  varieties  of  pure, 
hard  asphalt  were  examined  by  the  author,  one  having  a  black  color 
in  mass,  and  a  glossy,  black,  conchoidal  fracture :  another  having  a 
dark  brown  color  in  mass,  wTith  a  hackly,  dull  fracture.  They  tested 
as  follows: 

Black  Asphalt  Brown  Asphalt 

(Test   4)    Fracture Conchoidal  Hackly 

(Test    5)    Lustre Bright  Dull 

(Test    6)     Streak  on  porcelain Black  Yellowish  brown 

(Test    7)     Specific  gravity  at  77°  F 0.978 

(Test    9^)  Penetration  at  77°  F 10  2 

(Test    gc)  Consistency  at  77°  F 31.7  Above  i oo 

(Test  100)  Ductility  at  77°  F #  o 

(Test  15*)  Fusing-point  (K.  and  S.  method)  287°  F.  138°  F. 

(Test  1 6)    Volatile  at  500°  F.,  5  hrs 3  per  cent          1 . 15  per  cent 

(Test  19)     Fixed  carbon 10. 5  per  cent          9.4  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 98  per  cent  99  per  cent 

Mineral  matter 2  per  cent  i  per  cent 

(Test  37*)  Saponifiable  matter o  per  cent  o  per  cent 


154         NATIVE  ASPHALTS  OCCURRING  IN  FAIRLY  PURE  STATE       VIII 

The  brown  variety  is  unique.  It  is  somewhat  similar  in  physical 
properties  to  ozokerite,  but  it  is  very  much  more  friable.  When 
melted  it  turns  black  in  mass,  becoming  lustrous  (although  it  still 
shows  a  yellowish  brown  streak).  It  has  been  marketed  under  the 
name  "leyteite."  The  black  asphalt  is  not  classed  as  an  asphaltite 
in  view  of  its  comparative  softness  at  77°  F.  These  deposits  have 
not  yet  been  exploited  commercially. 


CHAPTER  IX 

NATIVE  ASPHALTS  ASSOCIATED  WITH  MINERAL 

MATTER 

This  chapter  will  include  the  principal  deposits  of  natural  as- 
phalts containing  10  per  cent  and  over  of  associated  mineral  matter, 
based  on  the  dry  weight.  Such  deposits  include  veins,  strata  and 
lake  formations. 

NORTH  AMERICA 

UNITED  STATES1 
Kentucky. 

All  the  deposits  in  the  State  of  Kentucky  are  composed  of  sand 
and  sandstone,  carrying  between  4  and  12  per  cent  of  soft  asphalt 
filling  the  interstices.2  These  deposits  occur  in  strata  from  5  to  40 
ft.  thick,  along  the  eastern  and  southeastern  border  of  the  coal  field 
in  Hardin,  Grayson,  Breckinridge,  Edmonson,  Hart,  Warren,  But- 
ler, Logan,  and  other  adjoining  counties. 

Hardin  County.  A  deposit  of  sand  asphalt  occurs  a  few  miles 
northeast  of  Summit,  in  the  southwestern  portion  of  Hardin  County. 

Carter  County.  This  deposit  occurs  one-half  mile  southeast  of 
the  town  of  Soldier,  and  consists  of  unconsolidated  quartz  grains 
held  together  by  4  to  10  per  cent  of  asphalt,  which  is  compara- 
tively soft  and  contains  a  goodly  proportion  of  volatile  matter. 

Breckinridge  County.  This  deposit  is  located  from  2  to  4  miles 
south  of  Garfield,  and  is  composed  of  unconsolidated  quartz  grains 
carrying  4  to  8  per  cent  of  asphalt  It  forms  a  hillside  ledge  about 
14  ft.  thick  with  an  overburden  of  10  to  20  ft.  The  deposit  has 
not  been  worked  to  any  great  extent  in  recent  years,  although  for- 
merly it  was  of  considerable  interest  in  the  paving  industry.  Other 
prospects  occur  in  this  neighborhood,  but  these  have  not  been  de- 
veloped* 

Grayson  County.  Two  deposits  have  been  worked  in  this  lo- 
cality in  the  vicinity  of  Big  Clifty  and  Grayson  Springs  Station,  one 

155 


156  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

3  miles  southwest,  and  the  other  9  miles  north  of  Leitchfield.  The 
former  occurs  in  a  stratum  5  ft.  thick,  impregnated  with  6  per  cent 
of  asphalt,  in  an  unconsolidated  quartz  sand.  The  second  was  for- 
merly one  of  the  most  active  mines  in  Kentucky,  but  has  now  been 
idle  for  a  number  of  years.  It  consists  of  a  stratum  10  ft.  thick, 
carrying  7-12  per  cent  of  very  soft  asphalt.  A  number  of  seepages 
are  in  evidence  along  the  side  walls  of  the  quarry  and  since  the 
asphalt  contains  a  large  proportion  of  volatile  matter,  they  soon 
harden  on  exposure  to  the  weather.  Some  of  the  seepages  exam- 
ined by  Richardson  contained  30  to  65  per  cent  of  mineral  matter, 
the  extracted  asphalt  showing  a  penetration  of  between  35  and  45 
at  77°  F.,  and  yielded  12  per  cent  of  fixed  carbon.  Another  deposit 
occurs  at  Tar  Hill. 

Edmonson  County.  Deposits  of  asphaltic  sandstone,  estimated 
to  exceed  200  million  tons,  covering  over  7000  acres,  are  located 
about  6  miles  due  west  of  Brownsville  and  about  12  miles  northeast 
of  Bowling  Green.  The  properties  adjoin  both  Bear  Creek  and 
Green  River,  being  located  on  both  sides  of  the  former  and  north 
of  the  latter.  Soil  overburden  of  5  to  40  ft.  covers  a  horizontal 
stratum  of  rock  asphalt  15  to  30  ft.  thick.  The  latter  analyzes  as 
follows : 

(Test  21)    Soluble  in  carbon  disulfide 4.22-    9.00  per  cent 

Matter  insoluble 95.64-  90.91  per  cent 

(Test  25)    Moisture  at  105°  C o.  14-    0.09  per  cent 

100.00  100.00  per  cent 

At  the  present  time  the  only  deposits  in  the  State  of  Kentucky 
worked  to  any  extent  occur  at  Kyrock  and  at  the  town  of  Asphalt, 
on  the  Nolin  River,  about  10  miles  west  of  the  celebrated  Mam- 
moth Cave,  near  Brownsville.  They  consist  of  a  stratum  of  fine  sand 
impregnated  with  8  to  10  per  cent  of  asphalt,  occurring  in  irregular 
beds  5  to  36  ft.  thick  in  a  horizontal  stratum  below  an  overburden 
of  clay  and  unimpregnated  sandstone,  6.  to  30  ft.  thick.  The  over- 
burden is  removed  by  a  hydraulic  pressure  line,  and  where  it  does 
not  yield  to  this,  a  steam  shovel  is  used.  The  rock  asphalt  is  re- 
moved by  quarrying  as  illustrated  in  Figs.  45  and  46,  and  conveyed 
by  a  gravity  tramway  to  a  crusher  which  reduces  the  rock  from  5-  to 
loin,  fragments  to  lumps  about  the  size  of  an  egg.  It  is  then 


NORTH  AMERICA 


157 


Courtesy  Kentucky  Rock  Asphalt  Co. 
FIG.  45. — Asphalt  Deposit  at  Kyrock,  Kentucky. 


Courtesy  Kentucky  Rock  Asphalt  Co. 
FIG.  46. — Hillside  Quarry  of  Kyrock  Asphalt  Deposit 


158  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

passed  through  a  battery  of  pulverizers,  illustrated  in  Fig.  47,  which 
further  reduces  the  rock  asphalt  to  small  grains  about  the  size  of 
corn  meal.  A  bucket  conveyor  transports  the  asphalt  to  barges  on 
the  Nolin  River,  which  in  turn  are  conveyed  down  to  the  Green 
River,  and  up  Barren  River  to  the  railroad  at  Bowling  Green.  It 
is  used  exclusively  for  paving  purposes,  and  is  reported  to  give  ex- 
cellent results. 

In  preparing  the  paving  mixture,  rocks  of  varying  asphalt  con- 
tent are  blended  to  obtain  a  product  carrying  uniformly  7  per  cent 
(±  y±  per  cent)  asphalt  soluble  in  carbon  disulfide.  In  applying 


Courtesy  Kentucky  Rock  Asphalt  Co. 
FIG.  47. — Pulverizing  Kentucky  Rock  Asphalt  at  Kyrock,  Kentucky. 

the  asphalt,  it  is  spread  loosely  over  the  primed  base  in  a  layer 
about  3  in.  thick  over  macadam  (9  to  10  in.  thick),  or  a  concrete 
base  (6  in.  thick),  and  compacted  cold  with  a  1 5-ton  steam  roller, 
to  a  thickness  of  2  in.,  provided,  however,  that  the  air  temperature 
is  not  lower  than  60°  F.  If  necessary,  the  surface  may  be  planed 
after  the  first  rolling,  by  which  the  excess  material  is  shaved  from 
the  high  places  and  deposited  in  the  depressions.  The  product  has 
the  advantages  of  not  requiring  a  hot  mixing  plant.  It  presents 
a  rather  gritty  surface,  which  prevents  slipping,  does  not  become 
svavy  under  traffic,  and  may  be  readily  repaired.  To  offset  these, 
it  has  the  disadvantage  of  being  marked  by  traffic  for  several  days 
after  being  laid,  and  moreover  it  is  claimed  that  the  drip  from 


IX  NORTH  AMERICA  159 

autos  readily  washes  out  the  asphalt  content,  leaving  unconsoli- 
dated  sand. 

Warren  County.  Several  deposits  of  sand  asphalt  are  located 
at  Youngs  Ferry  on  the  Green  River,  12  miles  north  of  the  town  of 
Bowling  Green.  One  occurs  in  a  bed  about  10  ft.  thick,  and  car- 
ries between  6  and  9  per  cent  of  asphalt  A  second  consists  of  a 
vein  5  to  15  ft.  thick  containing  about  the  same  percentage  of  as- 
phalt. Both  are  undeveloped.  The  extracted  asphalt  shows  a 
penetration  at  77°  F.  of  200,  and  much  volatile  matter  (13  per 
cent  at  400°  F.  in  seven  hours). 

Logan  County.  A  quarry  has  been  opened  up  about  5  miles 
northeast  of  Russellville,  exposing  about  15  ft.  of  asphaltic  sand- 
stone in  a  bed  about  100  ft.  long.  The  rock  carries  about  7  per 
cent  of  asphalt,  which  shows  very  much  less  volatile  matter  than 
the  preceding  (about  4  per  cent  loss  at  325°  F.  in  five  hours).  This 
mine  is  no  longer  active. 

Missouri.3 

Lafayette  County.  A  bed  of  asphaltic  sand  occurs  I J^  miles 
northwest  of  Higginsville,  carrying  8^  per  cent  of  asphalt,  asso- 
ciated with  sandy  shale.  This  deposit  has  not  been  worked  com- 
mercially. 

Indiana. 

While  drilling  for  oil  at  Princeton,  a  bed  of  asphalt  several  feet 
thick  was  found  100  ft.  below  a  vein  of  coal.  Seepages  of  liquid 
asphalt  have  also  been  reported  in  a  well  in  the  neighborhood. 
None  of  these  have  been  developed.* 

Oklahoma. 

This  state  is  one  of  the  richest  asphalt-bearing  centers  in  the 
United  States.  Asphalts  are  found  in  both  the  liquid  and  solid 
forms,  occurring  as  springs,  seepages  and  rock  impregnations.  Prac- 
tically all  the  deposits  are  found  in  the  southern  portion  of  the  state, 
between  the  35th  parallel  of  north  latitude,  and  the  Red  River  on 
the  south,  and  included  between  the  Arkansas  line  on  the  east,  to  the 
city  of  Granite,  Oklahoma,  on  the  west.  This  area  is  shown  in 
Fig.  48,  and  includes  deposits  or  prospects  in  the  following  counties : 
Comanche,  Jefferson,  Stephens,  Garvin,  Carter,  Murray,  Love, 
Marshall,  Johnston,  Pontotoc,  Atoka,  McCurtain  and  Leflore. 


160 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


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164 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


The  deposits  consist  of  asphaltic  sands,  asphaltic  limestone,  mix- 
tures of  the  two,  and  rarely  asphalt  impregnated  shale.  The  prin- 
cipal occurrences  are  included  in  Table  XVL5 

In  the  majority  of  cases  the  asphaltic  impregnation  is  of  liquid 
to  semi-liquid  consistency,  having  a  comparatively  low  fusing-point. 
It  is  contended  by  some  authorities  that  the  vast  deposits  of  sand 
asphalt  previously  constituted  oil-sands  which  have  been  laid  bare 
by  the  agencies  of  erosion,  faulting,  crumpling  and  upturning  of  the 


ASPHALT. 


I*  ••«!    AgptaH Sects. 

FIG.  48.— Map  of  Asphalt  Region  in  Oklahoma. 

strata,  so  that  the  lighter  oils  and  gases  have  escaped  into  the  air, 
leaving  the  sand  impregnated  with  the  comparatively  non-volatile 
asphaltic  constituents.  Most  of  the  deposits  occur  along  pronounced 
fault  lines,  although  faulting  is  not  essential,  since  certain  deposits 
haye  become  impregnated  by  the  uprising  of  asphalt-bearing  pe- 
troleum from  regions  below,  through  the  porous  sandstone  or 

limestone. 

A  characteristic  feature  of  these  deposits  is  the  sand  grains, 
which  are  round  and  unconsolidated,  being  held  together  by  the 
asphalt  filling  the  voids.  When  the  asphalt  is  extracted  the  grains 


IX 


NORTH  AMERICA 


165 


fall  apart,  and  show  the  same  general  characteristics  as  an  ordinary 
petroleum-bearing  sand. 

The  extent  of  these  deposits  has  been  variously  estimated  from 
2  to  13  million  tons.6 

Most  of  the  asphalt  mined  in  Oklahoma  has  been  used  for  pav- 
ing purposes,  and  the  author  has  seen  many  satisfactory  pavements 
laid  through  the  state  which  have  withstood  the  wear  and  tear 
of  traffic,  also  exposure  to  the  elements.  It  is  generally  necessary 
to  modify  the  rock  asphalts  either  by  combining  the  products  ob- 
tained from  different  deposits,  or  by  incorporating  pure  sand,  until 
a  proper  balance  is  obtained  between  the  asphalt  and  the  mineral 
constituents.  In  general,  the  best  results  have  been  obtained  with 
mixtures  containing  7  to  10  per  cent  of  asphalt  in  the  finished  paving 
composition. 

Numerous  water-extraction  plants  have  been  erected  to  separate 
the  asphalt  from  the  sand,  but  most  of  these  have  proven  unsuc- 
cessful, since  the  extraction  process  raises  the  price  of  the  refined 
asphalt  so  that  it  is  unable  to  compete  with  petroleum  asphalts  ob- 
tained from  other  sources  in  the  neighborhood. 

Tests  made  with  sand  asphalt  taken  from  the  quarry  in  Carter 
County,  Sec.  12  and  N  y2  Sec.  13,  T  3  S,  R  2  W,  18  miles  north- 
west of  Ardmore,  indicated  the  following.  The  dry  sand  asphalt 
contained  12.5  per  cent  of  pure  asphalt  having  a  fusing-point  (K. 
and  S.  method)  between  65  and  69°  F.  On  subjecting  it  to  the 
water-extraction  process,  the  following  results  were  recorded : 


Products 
Recovered, 
Per  Cent. 

Asphalt 
Content, 
Per  Cent. 

Total  Pure 
Asphalt, 
Per  Cent. 

6 

95 

£.7 

Impure  asphaltic  residue  

*? 

60 

1.8 

Separated  sand  waste  

9! 

2# 

2.3 

2.7 

Asphalt  in  crude  rock  

12.5 

Total          

IOO 

On  boiling  the  crude  rock  with  water,  impure  asphalt  rises  to  the 
surface,  and  the  "sarid  waste"  settles  to  the  bottom.    Upon  dehy- 


166 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


drating  the  impure  asphalt,  more  sand  settles  out,  constituting  what 
is  designated  uimpure  asphaltic  residue."  The  pure  asphalt  drawn 
off  from  this  residue  is  termed  "asphalt  recovered." 

The  "asphalt  recovered"  contained  5  per  cent  of  mineral  matter 
and  tested  as  follows: 

(Test    gb)  Penetration  at  32°  F 85 

Penetration  at  77°  F Over  360 

Penetration  at  115°  F Too  soft 

(Test    9<r)  Consistency  at  32°  F 10.0 

Consistency  at  77°  F i .  5 

Consistency  at  115°  F o.o 

(Test    gd)  Susceptibility  index 15 

(Test  1 5*)  Fusing-point  (K.  and  S.  method) 65-69°  F. 

(Test  15*)  Fusing-point  (R.  and  B.  method) 78-87°  F. 

(Test  16)    Volatile  at  500°  F.  in  5  hrs 10  per  cent 

Examination  of  Residue  (from  Test  16) 

(Test    9^)  Penetration  at  32°  F 7 

Penetration  at  77°  F 58 

Penetration  at  115°  F 250 

(Test    9^)  Consistency  at  32°  F 72-*> 

Consistency  at  77°  F 10.7 

Consistency  at  115°  F i .  I 

(Test    gd)  Susceptibility  index 63.  i 

(Test  io£)  Ductility  at  77°  F Over  100 

(Testi5*)  Fusing-point  (K.  and  S.  method) ii5°F. 

(Test  i$b)  Fusing-point  (R.  and  B.  method) 131°  F. 

Upon  evaporating  the  "asphalt  recovered"  at  250-260°  C,  the 
following  figures  were  recorded : 


Total  Loss,  Per  Cent. 


20 

25 
27 


Fusing-point  °F. 
(Test  15*) 


120 
125 

H7 
165 


Penetration  at  77°  F. 
(Test  gb) 


40 

19 
10 


A  sample  of  the  "asphalt  recovered"  upon  being  blown  with  dry 
air  at  300°  C.  for  nine  hours,  lost  23  per  cent  in  weight,  showed  a 
fusing-point  of  165°  F.,  and  a  hardness  at  77°  F.  of  38.0  (Test  9^), 
corresponding  to  a  penetration  at  77°  F.  of  8  (Test  gb).  It  is  ap- 
parent that  the  extracted  asphalt  is  scarcely  affected  by  blowing,  and 
thus  differs  from  asphalts  obtained  upon  distilling  petroleum.  It 


IX  NORTH  AMERICA  167 

has  been  reported  that  blowing  decreases  the  percentage  of  asphal- 
tous  acids,  anhydrides,  oily  constituents  and  resins.  The  molecular 
weight  of  the  resins  increases  from  733  to  1012  and  that  of  the 
asphaltenes  from  2219  to  4690  during  the  blowing  process.7  It 
has  been  further  corroborated  by  the  author's  observations  on  paints 
made  from  the  extracted  sand  asphalt,  which  were  found  to  be 
highly  resistant  to  atmospheric  oxidation.  A  sample  spread  on 
cloth  and  exposed  to  air  indoors  for  about  a  year,  showed  scarcely 
any  diminution  in  tackiness.8  Petroleum  asphalts  of  the  same  con- 
sistency when  tested  in  a  similar  manner,  dry  out  in  a  much  shorter 
time. 

A  mixture  containing  82' per  cent  of  the  uasphalt  recovered" 
fluxed  with  1 8  per  cent  of  grahamite,  showing  the  same  fusing-point 
(165°  F.),  tested  as  follows: 

(Test    7)    Specific  gravity  at  77°  F i  .09 

(Test    9^)  Penetration  at  1 15°  F 26 

Penetration  at  77°  F 17 

Penetration  at  32°  F 9 

(Test    9*)  Consistency  at  1 1 5°  F 14. 7 

Consistency  at  77°  F 27.  i 

Consistency  at  32°  F 65 . 4 

(Test    9</)  Susceptibility  index 30.7 

(Test  io£)  Ductility  at  115°  F 4.5 

Ductility  at  77°  F i.o 

Ductility  at  32°  F o.o 

(Test  11)    Tensile  strength  at  115°  F 1.8 

Tensile  strength  at  77°  F 6.5 

Tensile  strength  at  32°  F 9.5 

(Test  15*)  Fusing-point  (K.  and  S.  method) 165°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 183°  F. 

(Test  16)    Volatile  at  500°  F.  in  5  hrs o. 5  per  cent 

Arkansas. 

Seven  to  eight  known  deposits  of  asphalt  occur  in  southwestern 
Arkansas,  in  Pike  and  Sevier  Counties,  only  one  of  which  has  been 
developed  into  a  mine  producing  commercial  quantities.  This  is 
located  2l/2  miles  south-southeast  of  Pike,  in  Pike  County.0  The 
asphalt  impregnates  nearly  horizontal  strata  of  unconsolidated 
sand,  except  in  one  locality,  where  it  impregnates  gravel.  The  veins 
run  from  i  in.  to  12  ft.  thick. 

Pike  County.  The  most  important  deposit  occurs  on  the  west 
side  of  the  road  connecting  the  towns  of  Pike  and  Delight,  about 
2  y2  miles  south-southeast  of  Pike.  It  has  been  mined  in  an  open 


168  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

cut  100  ft  wide,  200  ft.  long  and  15  ft.  deep.  The  sand  carries 
from  5  to  1 6  per  cent  asphalt,  averaging  7^2  per  cent,  and  is  used 
for  paving  purposes.  Prospects  occur  about  4  miles  north-north- 
west of  Delight  in  a  bed  3  to  5  ft.  thick,  carrying  up  to  17  per  cent 
asphalt  associated  with  sand  carrying  a  few  nodules  of  iron  pyrites; 
also  about  I  mile  northeast  of  Murfreesboro,  on  the  east  bank  of 
Prairie  Creek,  in  which  the  asphalt  impregnates  gravel. 

Sevier  County.  Prospects  occur  y*  mile  southeast  of  Lebanon, 
alongside  of  the  road  adjoining  the  Salina  River  bottom,  in  len- 
ticular formations  up  to  i  ft.  thick;  another  about  2l/2  miles  west- 
southwest  of  Lebanon;  another  on  the  south  side  of  the  road  4 
miles  west-southwest  of  Lebanon;  and  still  another  6y2  miles  west- 
southwest  of  Lebanon  along  the  road  just  northwest  of  Moody 
Shoal  Ford  on  Cossatot  River. 

Alabama. 

An  area  occurs  in  northern  Alabama  measuring  about  72  miles 
by  8  miles  in  which  i  to  15  per  cent  of  asphalt  is  associated  with 
unconsolidated  sand  granules.  It  extends  through  the  following 
counties : 10 

Colbert  County.  A  fairly  extensive  deposit  of  sand  asphalt  has 
recently  been  developed  near  Florence,  on  the  banks  of  the  Ten- 
nessee River,  in  the  vicinity  of  Muscle  Shoals,  which  has  been  used 
in  the  vicinity  for  paving  purposes.  Another  deposit  occurs  i  mile 
south  of  Margerum,  on  the  Southern  Railroad,  writhin  an  area  3 
miles  square,  consisting  of  asphaltic  limestone.  Others  have  been 
reported  2  miles  southeast  of  Cherokee,  consisting  of  asphaltic 
limestone  and  sand;  likewise  sand  asphalt  deposits  i  to  7  miles  east 
of  Littleville,  and  at  Leighton  and  Russelville  (extending  into 
Franklin  County). 

Lawrence  County.  Asphalt  sand  is  found  at  Wolf  Springs  on 
the  summit  of  Little  Mountain,  about  6  miles  southwest  of  Town 
Creek  Station  on  the  Southern  Railroad.  Another  deposit  occurs 
at  Caddo,  midwray  between  Moulton  and  the  Morgan  County  line, 
in  the  southeast  section. 

Morgan  County.  A  sand  asphalt  deposit  occurs  about  3  miles 
northwest  of  Flint  Station  on  the  L.  &  N.  Railroad,  and  another 
in  the  vicinity  of  Hartsville,  to  the  east  and  southeast  thereof. 


IX  NORTH  AMERICA  169 

Louisiana. 

Lafayette  Parish.  A  sand  asphalt  deposit  has  recently  attracted 
attention  about  5  miles  from  Lafayette,  covering  about  50  acres  on 
the  surface.11 

Texas.12 

Montague  County.  Deposits  are  reported  3  to  3  J4  miles  north- 
east of  the  City  of  St.  Jo,  carrying  between  5  and  1 1  per  cent  of 
asphalt,  averaging  in  the  neighborhood  of  7  per  cent,  although  the 
percentage  varies  in  different  localities.  They  contain  sandstone, 
or  a  mixture  of  sandstone  and  limestone,  but  are  of  no  commercial 
importance. 

Burnet  County.  This  occurrence  is  at  Post  Mountain  near  the 
town  of  Burnet,  and  consists  of  an  asphaltic  limestone,  containing 
about  10  per  cent  of  asphalt  of  a  very  soft  consistency  (having  a 
penetration  of  20-250  at  77°  R). 

Uvalde  County.  The  most  important  Texas  deposits  are  found 
in  the  southwestern  part  of  this  county  near  Cline,  about  18  to  25 
miles  west  of  the  city  of  Uvalde,  in  the  region  of  the  Anacacho 
Mountains.  They  consist  of  limestone,  carrying  10  to  20  per  cent 
of  asphalt,  averaging  about  15  per  cent  Crystalline  calcite  is  pres- 
ent, also  numerous  fossil  remains  of  molluscs,  indicating  the  asphalt 
to  be  of  animal  origin.  The  deposits  have  been  traced  for  several 
miles,  but  their  exact  extent  is  not  accurately  known.  A  large  quan- 
tity has  been  quarried,  and  from  recent  reports  the  mines  are  still 
being  operated.  The  impregnating  asphalt  is  quite  hard,  showing 
a  conchoidal  fracture  and  brilliant  lustre.  It  has  a  moderately 
high  fusing-point,  and  analyzes:  carbon  81  per  cent,  hydrogen  12 
per  cent,  sulfur  6^2  per  cent,  nitrogen  l/2  per  cent;  total  100  per 
cent.  The  rock  asphalt  is  too  hard  for  a  paving  material  if  used 
alone.  It  is  therefore  mixed  with  about  25  per  cent  of  trap  rock 
and  the  requisite  amount  of  flux.  The  mixture  is  adapted  to  be 
rolled  cold  in  surfacing  a  pavement.  One  ton  will  cover  20  sq.  yd. 
I  in.  thick.  Fig.  49  illustrates  the  principal  mine,  with  about  80,000 
tons  of  asphalt  rock  blasted  loose  and  ready  to  be  loaded  into  the 
cars  by  the  steam  shovel.  It  is  then  transported  to  the  mixing  and 
crushing  plant.  Fig.  50^  shows  the  equipment  for  crushing  and 
screening  the  rock  asphalt;  Fig.  $oB  the  device  for  mixing  the  trap 


170 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


rock  with  the  rock  asphalt;  and  Fig.  5oC  shows  a  42  cu.  ft.  capacity 
twin  pug-mill  which  is  used  for  pulverizing  the  asphalt.  The  pure 
asphalt  extracted  from  the  rock  has  been  marketed  under  the  name 
"litho-carbon"  13  which  may  also  be  blown.  This  constitutes  the 
most  important  deposit  in  Texas. 


Courtesy  Uvalde  Asphalt  Compan;. 
FIG.  49.  —  Rosk-asphalt  Quarry  in  Uvalde  County,  Texas. 

Litho-carbon  shows  the  following  tests  : 


Color  in  mass  .....  .  .  .  .  ......  .................  Black 

Fracture  ...................................  Conchoidal 

Lustre...  ......  .....  .......................  Bright 

Streak  .....................................  Brownish  black 

Specific  gravity  at  77°  F  ......................  i  •  ^9 

Penetration  at  115°  F  ........  ................  16 

Penetration  at  77°  F  .........................  4 

Fusing-point  (K.  and  S.  method)  ..............  1  16°  F. 

Volatile  at  500°  F.,  in  5  hours  .................  2.76  per  cent 

Soluble  in  carbon  disulfide  .....................  96  .  35  per  cent 

Non-mineral  matter  insoluble  .................       0.75  per  cent 

Mineral  matter  ...........  ...................       ^-9Q  per  cent 


(Test  i) 

(Test  2) 

(Test  3) 

(Test  4) 

(Test  7) 

(Test  9^) 

(Test  15*) 
(Test  16) 
(Test  21) 


100  .  oo  per  cent 
(Test  23)     Soluble  in  88°  petroleum  naphtha  .............     53  .08  per  cent 

Other  deposits  of  the  same  general  character  are  found  in  the 
neighborhood.     One  20  miles  south-southwest  of  Uvalde  and  5 


IX 


NORTH  AMERICA 


171 


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0- 


1  a 

IB 

a> 


2 
75 

tD 

i 


172  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

miles  south  of  the  preceding  quarry  showed  12  per  cent  of  asphalt 
with  17  per  cent  of  fixed  carbon. 

Kinney  County.  The  Uvalde  deposits  extend  westward  into 
Kinney  County,  with  outcroppings  near  Blewett,  where  mining  op- 
erations have  been  undertaken. 

Anderson,  Jasper,  and  Cooke  Counties.  Minor  deposits  are 
reported  in  these  counties,  but  are  of  no  commercial  value.1 


14 


Utah. 

Carbon  County.19  A  deposit  of  asphaltic  limestone  occurs  at 
the  head  of  the  right-hand  branch  of  Pie  Fork,  a  canyon  northwest 
of  the  town  of  Clear  Creek.  The  rock  is  non-uniform  in  composi- 
tion, some  containing  between  6  and  14  per  cent  of  asphalt  (having 
a  penetration  at  77°  F.  of  7  to  15),  and  some  as  high  as  75  per 
cent  (showing  a  penetration  at  77°  F.  of  45)  with  scarcely  any 
fixed  carbon.  Another  deposit  of  asphaltic  sand  has  been  reported 
8  miles  from  Sunnyside  on  the  tributaries  of  Whitmore  Canyon, 
in  the  Brook  Cliffs  on  the  West  Tavaputs  Plateau,  carrying  1 1  per 
cent  of  soft  asphalt,  which  upon  being  extracted  tested  as  follows: 

(Test  16)    Volatile  at  325°  F.,  5  hrs 6.6  per  cent 

(Test  19)    Fixed  carbon 5.0  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 91 . 8  per  cent 

Utah  County.  A  large  area  underlaid  with  asphaltic  limestone 
occurs  just  north  of  Colton,  and  south  of  Strawberry  Creek,  extend- 
ing from  Antelope  Creek  on  the  east  to  Thistle  on  the  west.  The 
principal  deposit  is  at  the  town  of  Asphalt,  carrying  12  per  cent  of 
asphalt. 

Grand  County.  At  the  head  of  the  West  Water  Canyon  about 
20  miles  north  of  the  town  of  West  Water,  there  is  an  asphaltic 
limestone  deposit  containing  50  per  cent  asphalt  and  50  per  cent 
limestone.  Investigations  indicate  that  this  asphalt  is  a  progenitor 
of  gilsonite.  The  extracted  asphalt  is  reported  by  Clifford  Rich- 
ardson to  test  as  follows : 

(Test   7)    Specific  gravity  at  77°  F 1 .037 

(Test   oi)  Penetration  at  77°  F 22 

(Test  16)    Volatile  at  212°  F 2.8  per  cent 

(Test  19)    Fixed  carbon ' 8  .o  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha 88.7  per  cent 


IX  NORTH  AMERICA  173 

Vint  a  County.  The  largest  deposit  of  asphaltic  sandstone 
occurs  3  to  4  miles  southwest  of  Vernal,  north  of  the  Green  River, 
between  the  Ashley  and  Uinta  Valleys,  in  an  outcrop  about  nl/2 
miles  long,  known  as  "Asphalt  Ridge."  16  It  contains  8  to  15  per 
cent  by  weight  of  asphalt,  averaging  11^2  per  cent  A  typical 
specimen  analyzed  as  follows: 

(Test  21)     Soluble  in  carbon  disulfide 12.8  per  cent 

Mineral  matter  on  ignition 86.45  per  cent 

(Test  16)    Volatile  at  105°  C.  in  i  hour 0.20  per  cent 

The  extracted  asphalt  tested  as  follows: 

(Test    7)    Specific  gravity  at  77°  F 0.980 

(Test  19)     Fixed  carbon 7.1  per  cent 

* 

The  asphalt'  has  been  used  successfully  just  as  it  is  mined,  for 
paving  the  streets  of  Vernal. 

Another  deposit,  or  rather  a  series  of  deposits,  occur  in  Argyle 
Creek,  a  tributary  of  the  Minnie  Maud  Creek,  which  in  turn  flows 
into  the  Green  River  about  20  miles  south  of  Ouray.  The  ma- 
terial consists  of  an  asphaltic  sandstone,  exploited  under  the  name 
"argulite,"  carrying  between  8  and  10  per  cent  of  asphalt.  The 
extracted  asphalt  tests  as  follows : 

(Test    5)    Lustre Bright 

(Test    6)     Streak Black 

(Test   7)    Specific  gravity  at  77°  F o.  997-1 .013 

(Test    9^)  Penetration  at  77°  F 14 

(Test  16)    Volatile  at  325°  F.  in  5  hrs 25. 8  per  cent 

(Test  19)    Fixed  carbon 8.55 

(Test  23)     Soluble  in  88°  petroleum  naphtha , 88 

(Test  26)    Carbon 89.9  per  cent 

(Test  27)    Hydrogen 9.0  per  cent 

(Test  28)    Sulfur o.o  per  cent 

(Tests  29  and  30)  Nitrogen  and  oxygen i .  i  per  cent 


Total 100.0  per  cent 

(Test  340)  Saturated  hydrocarbons 25     per  cent 

Wyoming. 

Fremont  County.  Asphalt  and  semi-solid  asphalt  seepages 
were  used  for  many  years  as  fuel  by  shepherds  on  Copper  Moun- 
tain in  section  T.  4  N.,  R.  92—93  W.,  in  northeastern  Fremont 
County. 


174 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


California,17 

Mendocino  County.  Deposits  of  asphaltic  sand  are  found  2 
miles  north  of  the  town  of  Point  Arena  and  l/2  mile  from  the  coast, 
carrying  between  6  and  7  per  cent  of  asphalt.  A  similar  deposit 
occurs  just  north  of  Port  Gulch. 

Santa  Cruz  County.     Large  deposits  of  asphalt  sand  occur  4  to 


FIG.  51. — Sand  Asphalt  Quarries  in  Santa  <Jruz  county,  v;ai. 

6  miles  northwest  of  the  city  of  Santa  Cruz,  near  the  summit  of 
Empire  Ridge,  a  spur  of  the  Santa  Cruz  Mountains,  3^  miles 
from  the  coast.  A  number  of  quarries  have  been  opened  up  in  this 
region,  and  the  product  used  for  constructing  pavements  in  Santa 
Cruz  and  San  Francisco.  The  rock  contains  between  10  and  17^ 
per  cent  asphalt  of  variable  hardness,  containing  a  substantial  pro- 
portion of  volatile  matter.  The  veins  vary  from  2  to  32  ft  thick, 


IX 


NORTH  AMERICA 


175 


as  shown  in  Figs.  51  and  52.  Three  strata  are  found,  an  upper 
8  ft  thick  containing  2-3  per  cent  asphalt,  a  middle  one  32  ft. 
thick  containing  14  per  cent  asphalt,  and  a  lower  25  ft.  thick  carry- 
ing 1 6-1 8  per  cent  asphalt. 

Monterey  County.  Several  deposits  of  asphaltic  sandstone  are 
scattered  throughout  the  Salinas  Valley.  A  prospect  occurs  about 
10  miles  from  King  City,  composed  of  particles  of  quartz,  feldspar 
and  mica,  impregnated  with  a  varying  percentage  of  asphalt.  An- 
other deposit  occurs  7  miles  southeast  of  Metz  at  the  head  of 


A-UJ.  5*. — oanu  -mspnair  uuarnes  in  Santa  Cruz  County,  Cal. 

Chelone  Creek,  of  the  same  general  character.  A  large  vein,  about 
125  ft.  thick  and  3  miles  long,  has  been  reported  near  San  Ardo, 
composed  of  coarse  quartz  grains,  and  a  little  feldspar,  impregnated 
with  a  small  percentage  of  asphalt. 

San  Luis  Obispo  County.  Sand  asphalt  deposits  occur  about 
80  miles  southwest  of  the  town  of  San  Luis  Obispo,  consisting  of 
a  number  of  actively  worked  quarries.  The  rock  is  fine  grained,  of 
even  texture,  consisting  mostly  of  quartz,  with  a  small  quantity  of 
feldspar.  The  percentage  of  asphalt  varies  from  8  to  18  per  cent, 
averaging  about  10. 


176  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

+ 

Santa  Barbara  County.  Santa  Maria  Region.  Associated 
with  the  pure  asphalt  deposits  already  described*  zones  of  asphalt- 
impregnated  shale  have  been  reported  on  the  western  slope  of  the 
Azufre  Hills,  containing  30  to  40  per  cent  of  asphalt. 

Sisquoc  Region.  Deposits  of  sand  asphalt  occur  in  the  neigh- 
borhood of  the  town  of  Sisquoc,  carrying  between  14,  and  18  per 
cent  of  asphalt.  The  largest  vein  occurs  in  Bishop's  Gulch,  about 
100  ft.  thick,  running  fairly  uniform  in  composition.  'Some  time 
ago  an  attempt  was  made  to  remove  the  asphalt  by  extraction  with 
solvents,  but  the  process  proved  too  costly  and  had  to  be  abandoned. 
Similar  deposits  are  found  in  the  neighborhood  of  La  Brea  Creek, 
where  a  vein  of  sand  asphalt  occurs  20  to  60  ft.  thick;  also  at  Los 
Alamos  Creek. 

Gaviota  Region.  A  prospect  has  been  reported  in  this  locality 
consisting  of  a  bed  of  sandstone  and  conglomerate  about  25  ft. 
thick,  containing  7  to  8  per  cent  of  asphalt. 

Mores'  Landing,  This  deposit  is  found  on  the  seacoast  about*  7 
miles  west  of  Santa  Barbara,  occurring  as  veins  and  irr$gul||  masses 
in  massive  sandstone  cliffs,  at  least  too  ft.  thick.  Acceding  to 
Eldridge  it  contains  30  to  60  per  cent  of  asphalt  and  has  a  strong 
resemblance  in  structure,  brilliancy,  and  fracture  to  gilsonite,  al- 
though it  is  very  much  softer  in  consistency. 

La  Patera  Region.  A  vein  of  asphalt  of  historical  interest  only, 
occurs  about  10  miles  west  of  Santa  Barbara,  close  to  the  coast.  It 
varies  in  width  from  2  to  12  ft,  with  a  number  of  lateral  branches 
several  inches  thick.  The  asphalt  is  associated  with  30  to  50  per 
cent  of  mineral  matters  composed  of  shale,  sand,  and  clay.  It  is 
stated  that  30,000  tons  have  been  removed  from  this  mine,  testing, 
when  dried,  as  follows : 18 

(Test   4)    Fracture Irregular 

(Test    5)    Lustre Dull 

(Test   6)    Streak *.-.  Black 

(Test   7)    Specific  gravity  at  77°  F i  .38 

(Test   94)  Hardness  on'Moh's  scale 1 

(Test   9$)  Penetration  at  77°  F o 

(Test  16)    Volatile  at  400°  F.,  5  hrs 2, 5  per  cent 

(Test  19)    Fixed  carbon 14,9  per  cent 

(Test  a i)    Soluble  in  carbon  disulfide Approx.  50  per  cent 

Mineral  matter. . ,. i  •  •  v  •  Ab°ut  5°  per  cent    ., 

(Test  13)    Soluble  in  88°  petroleum  naphtha 21 , 6  per  cent 

(T*stl8)    Sulfur ^ ,-, 6,2  per  cent  >\ 

(Test  34*)  Saturated  hydrocarbons 8.  i;per  cent  r 


IX 


NORTH  AMERICA 


177 


Carpinteria  Region.  This  deposit,  composed  of  asphaltic  sand 
about  15  ft.  thick,  lying  along  the  ocean's  shore  at  Benham,  2  miles 
southeast  of  Carpinteria,  is  illustrated  in  Fig.  53.  It  contains  18  to 
20  per  cent  of  asphalt  filling  the  interstices  of  unconsolidated  quartz 
grains.  Some  time  ago  a  process  was  installed  for  extracting  the 
asphalt  with  water,  but  this  never  proved  successful  commercially. 


FIG,  53. — Asphaltic  Sand  on  the  Shore  at  Carpinteria,  Cal. 

Orange  County*  Bituminous  sands  have  been  reported  4  miles 
southwest  of  Chino,  in  a  layer  about  6  ft.  thick,  containing  varying 
percentages  of  asphalt. 

CANADA 
Alberta  Province. 

McMurray  Region.  Vast  deposits  of  asphaltic  sands  occur  on 
both  banks  of  the  Athabaska  River,  and  its  tributary,  the  Clear 
Water  River,  covering  probably  not  less  than  750  square  miles.19 
The  deposit  varies  in  thickness  to  a  maximum  of  225  ft.  Character- 
istic views  of  the  outcrop  on  the  Athabaska  River  are  shown  in 
54  (A  and  B).  The  material  contains  12  to  20  per  cent  as- 


178  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

phalt,  averaging  between  15  and  18  per  cent,  associated  with  an 
unconsolidated  sand  consisting  of  betwreen  93  and  99  per  cent  pure 


(B) 

Courtesy  S.  C.  Ells. 

FIG.  54. — Asphaltic  Sand  on  Banks  of  Athabaska  River,  Alberta,  Can. 

silica.  A  marked  variation  in  the  size  of  the  sand  grains  is  charac- 
teristic of  almost  every  exposed  section  of  the  deposit,  ranging  from 
40  to  80  mesh.  The  asphalt  is  amenable  to  the  water  extraction 


IX  NORTH  AMERICA  179 

process.     A  specimen  of  the  extracted  asphalt  examined  by  the 
author  tested  as  follows: 

(Test   7)    Specific  gravity  at  77°  F 1.022 

(Test    9^)  Penetration  at  77°  F Too  soft  for  test 

Penetration  at  32°  F 120 

(Test   9^)  Consistometer  hardness  at  1 15°  F o.o 

Consistometer  hardness  at  77°  F o.o 

Consistometer  hardness  at  32°  F 2.7 

(Test  io*)  Ductility  at  115°  F 2.0 

Ductility  at  77°  F 7?o 

Ductility  at  32°  F 12.5 

(Test  154)  Fusing-point  (K.  and  S.  method) 50°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 63°  F. 

(Test  16)    Volatile  at  500°  F.  in  5  hrs 17.9  per  cent 

Volatile  at  325°  F.  in  5  hrs *  1 1 . 2  per  cent 

(Test  19)    Fixed  carbon 7,23-10. 55  per  cent 

(Test  21)    Soluble  in  carbon  disulfide. 97.3    per  cent 

Mineral  matter 2.7    per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 78 . 2    per  cent 

(Test  26)     Carbon 84.49  per  cent 

(Test  27)     Hydrogen 1 1 . 23  per  cent 

(Test  28)     Sulfur 2 . 73  per  cent 

(Test  29)    Nitrogen 0.04  per  cent 


Total 98 .49  per  cent 

(Test  340)  Saturated  hydrocarbons 39.6    per  cent 

The,  non-volatile  matter  tested  as  follows : 

Residue  at 
500°  F.  325°  F. 

(Test   7)    Specific  gravity  at  77°  F 1.028  1.021 

(Test    gb)  Penetration  at  115°  F no  

Penetration  at  77°  F 62  262 

Penetration  at  32°  F 18  

(Test   9^)  Consistency  at  115°  F 3.7  

Consistency  at  77°  F 8.5  

Consistency  at  32°  F 49 . 3  

(Test   gd)  Susceptibility  index 36. 5  

(Test  lot)  Ductility  at  115°  F 34. 5  +100 

Ductility  at  77°  F 45.0  +100 

Ductility  at  32°  F 0.5  

(Test  1 1)    Tensile  strength  at  115°  F 0.3  

Tensile  strength  at  77°  F 1.5  

Tensile  strength  at  32°  F 25. 5  

(Test  150)  Fusing-point  (K.  and  S.  method).  125°  F.  106°  F. 

(Test  15*)  Fusing-point  (R.  and  B.  method)  142°  F.  121°  F. 

(Test  19)    Fixed  carbon 12.33  P61"  cent        8.99  per  cent 

A  sample  of  extracted  Alberta  asphalt  having  a  K.  and  S. 
fusing-point  of  84°  F.  was  blown  2l/2  hours  at  500°  F.  during  which 


ISO  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

process  it  lost  17  per  cent  in  weight,  and  the  resultant  product  tested 
as  follows: 

(Test    5)    Lustre. Bright'and  tough 

(Test   g&)  Penetration  at  115°  F 5.6 

Penetration  at  77°  F 3.0 

Penetration  at  32°  F i  .o 

(Test  150)  Fusing-^point  (K.  and  S.  method) 208°  F. 

A  duplicate  sa'mple  was  evaporated  in  air  until  it  lost  exactly 
1 7  per  cent  by  weight,  whereupon  the  residue  showed  a  f  using-point 
of  128°  F.  (K.  and  S.),  demonstrating  that  the  material  was  sus- 
ceptible to  the  process  of  blowing. 

The  crude  asphalt,  after  being  tempered  with  additional  pure 
sand  to  reduce  the  percentage  of  asphalt,  has  given  successful  results 
for  paving  purposes  in  Edmonton,  Canada.  ( 

Manitoba  Province.  Similar  deposits  are  reported  to  occur  in 
the  Clear  River  District  in  this  province.20 

MEXICO 

States  of  Vera  Cruz  and  Tamaulipas.  Several  deposits  of 
sand  asphalt  have  been  reported  in  the  neighborhood  of  Tampico 
and  Vera  Cruz,  containing  8  to  14  per  cent  of  asphalt,  but  none 
have  been  developed  commercially. 

CUBA2* 

Province  of  Matanzas.  Semi-solid  asphalts  have  been  mined  for 
many  years  at  the  bottom  of  Cardenas  Harbor,22  The  most  im- 
portant deposit,  known  as  the  uConstancia  Mine,"  occurs  about  12 
ft.  below  the  level  of  the  water,  and  is  consequently  mined  with 
difficulty.  Other  deposits  of  semi-liquid  asphalt  containing  more  or 
less  mineral  matter,  occur  at  the  mouth  of  the  La  Palma  River, 
about  20  miles  from  Cardenas;  also  near  Sabanilla  de  la  Palma, 
about  30  miles  east  of  Cardenas  and  4  to  5  miles  west  of  Hato 
Nuevo.  Analyses  are  not  available. 

Province  of  Pinar  del  Rio.  Deposits  of  sand  asphalt  have  been 
reported  at  Bahia  Honda  and  Mariel,  in  the  neighborhood  of 
Mariel  Bay>  also  at  Vuelta  Abajo.  No  analyses  are  available. 

Province  of  Havana.    An  extensive  deposit  approaching  glance 


IX  NORTH  AMERICA  181 

pitch  in  properties,  known  as  the  uAngelo  Elmira  Mine/'  has  been 
found  near  Bejucal,  about  18  miles  south  of  Havana,  associated 
with  mineral  matter  composed  of  calcium  carbonate,  silica,  and  sili- 
cates, which,  according  to  Clifford  Richardson,28  tests  as  follows : 

(Test   i)    Color  in  mass Brownish  black  to  black 

(Test  4)    Fracture SemUconchojdal  to  conchoidal 

(Test   5)    Lustre Dull 

(Test  6)    Streak Reddish  brown  to  brown 

(Test  7)    Specific  gravity  at  77°  F i .  30-1 . 35 

(Test   9*)  Hardness,  Moh's  scale 2-3 

(Test  9*)  Hardness,  penetrometer  at  77°  F. . .  o 
(Test  16)    Volatile  at  325°  F.,  5  hrs,  (dry  sub- 
stance)    About  i  per  cent 

Volatile  at  400°  F.,  5  hrs.  (dry  sub- 
stance)   About  i#  per  cent 

(Test  19)    Fixed  carbon 17.4-25.0  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 70-75     percent 

Non-mineral  matter  insoluble 3#-  4     per  cent 

Mineral  matter  (calcium  carbonate, 

etc.) 21-18     per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha, .      32-50     per  cent 
(Test  28)    Sulfur About  8.3  per  cent 

Five  miles  east  of  Bejucal,  there  is  another  deposit,  similar  to 
the  preceding. 

Province  of  Camaguey,  Impure  soft  and  hard  asphalt  deposits 
are  found  near  Minas,  a  small  town  about  30  miles  from  Nuevitas, 
and  20  miles  from  Puerto  Principe. 

Province  of  Santiago  de  Cuba.  A  deposit  of  hard  impure 
asphalt  occurs  5  to  10  miles  south  of  Puerto  Padre  in  Victoria  de 
las  Tunas  district,  testing  as  follows  : 

(Test   i)    Color  in  mass Black 

(Test  4)    Fracture Hackly 

(Test   5)    Lustre Dull 

(Test  6)    Streak Dark  brown 

(Test  7)    Specific  gravity  at  77°  F 1 . 106 

(Test   94)  Hardness,  Moh's  scale I    . 

(Test  19)    Fixed  carbon 9.9  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 78.4  per  cent 

Non-mineral  matter  insoluble 18.2  percent 

Mineral  matter , 3,4  per  cent 

Total 100,0  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha ,,..,,.,.,.  60, 6  per  cent 


182 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


SOUTH  AMERICA 
TRINIDAD 

St.  Patrick  County.  One  of  the  largest  deposits  of  asphalt  in 
the  entire  world  occurs  on  the  Island  of  Trinidad  24  on  the  north 
coast  of  South  America,  situated  a  short  distance  from  the  main- 
land of  Venezuela,  between  the  Caribbean  Sea  on  the  west  and  the 
Atlantic  Ocean  on  the  east. 

Small  deposits  are  scattered  all  over  the  Island,  but  the  largest 
one  known  'as  the  "Trinidad  Asphalt  Lake/'  is  situated  on  La  Brea 
Point,  in  the  Wards  of  La  Brea  and  Guapo,  on  the  western  shore. 
The  lake  is  situated  on  the  highest  part  of  La  Brea  Point,  138  ft. 
above  sea  level.  It  covers  an  area  nearly  circular  comprising  115 
acres,  in  a  slight  depression  or  shallow  crater  at  the  crest  of  the 
hill.  The  exact  location  of  the  lake  is  shown  in  Fig.  55.  The  lake 

measures  about  2000  ft.  across 
and  is  over  135  ft.  deep  in  the 
center,  becoming  shallower  to- 
wards the  edges.  A  panoramic 
view  is  shown  in  Fig.  56. 

The  asphalt  surface  is  broken 
up  into  a  series  of  large  folds  with 
accumulations  of  rain  water  in  the 
creases.  A  typical  view  is  shown 
in  Fig.  57.  The  entire  mass  of 
asphalt  is  in  constant  but  slow  mo- 
tion from  the  center  towards  the 
edges,  probably  due  to  the  con- 
tinual influx  of  solid  material  at 
the  center,  accompanied  by  a 
strong  evolution  of  gas  which  im- 
parts a  porous  or  honeycombed 
structure.  The  evolution  of  gas 
through  the  water  is  shown  in  Fig,  58.  Wherever  a  hole  is  dug  in 
the  surface,  it  slowly  fills  up  and  disappears.  The  asphalt  is  softest 
in  the  center  of  the  deposit,  and  gradually  hardens  towards  the 
circumference.  Even  in  the  center,  the  consistency  is  such  that  it 


\3*fo     ^ 

\{    Vyo 

V  V .._.  M«i>*tffnjffl 

••^^ 


NwaWt.     t 
foileaad  track 


FIG*  55. — Map  of  Trinidad  .Asphalt  Lake. 


IX 


SOUTH  AMERICA 


183 


O 

Is 


J 


12 
*3 

5 


O 

c 

el 

°[ 

vo 

& 


184 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


Courtesy  of  Barber  Co, 
FIG.  57.— Folds  in  the  Surface  of  Trinidad  Lake. 


Courtesy  of  Barber  Co. 
FIG.  58.— Evolution  of  Gas  from  Trinidad  Lake. 


IX 


SOUTH  AMERICA 


185 


will  bear  the  weight  of  a  man,  and  can  be  readily  broken  out  in 
large  masses  with  picks  as  shown  in  Fig.  59. 

Shrubs  and  small  trees  grow  on  the  surface  in  isolated  patches 
known  as  "islands,"  which  slowly  migrate  from  place  to  place  with 


Courtesy  of  Barber  Co. 


FIG.  59. — Gathering  Trinidad  Lake  Asphalt. 


Courtesy  of  Barber  Co. 
FIG,  60. — Transporting  Trinidad  Lake  Asphalt. 

the  movement  of  the  asphalt.    Grassy  vegetation  extends  along  the 
edges  of  the  lake  merging  into  the  surrounding  country. 

The  crude  asphalt  is  loaded  on  small  cars  run  by  cable  over  the 
lake  in  a  loop,  the  rails  being  supported  by  wooden  ties  which  must 
be  replaced  from  time  to  time  as  they  gradually  sink  into  the  surface 
of  the  asphalt.  The  asphalt  is  transferred  to  an  inclined  cable  way 


J86  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

at  the  end  of  the  loop  which  runs  to  the  shore,  and  thence  to  a  long 
pier  where  it  is  dumped  on  board  steamers  (Fig.  60). 

It  has  been  estimated  that  the  lake  still  contains  10  to  15  million 
tons  of  asphalt.  Although  vast  quantities  have  been  removed  in 
the  past,  the  level  of  the  lake  has  not  sunk  more  than  8  to  10  ft, 
since  the  rate  of  influx  closely  approximates  the  quantity  removed. 
In  the  past  ten  years  approximately  10  million  tons  of  asphalt  have 
been  removed,  during  which  period  the  level  has  sunk  approximately 
il/2  meters. 

The  fresh  material  consists  of  an  emulsion  of  asphalt,  gas,  water, 
sand  and  clay.  According  to  Clifford  Richardson  25  oil  sands  occur- 
ring at  a  depth  carry  an  asphaltic  petroleum  and  natural  gas  under 
high  pressure,  which  on  coming  in  contact  with  a  paste  of  colloidal 
clay  and  silica  are  converted  into  the  asphalt  which  emerges  at  the 
surface. 

The  crude  Trinidad  Lake  asphalt  is  extremely  uniform  in  com- 
position, as  is  evident  from  analyses  of  samples  taken  from  different 
points  over  the  surface,  calculated  on  a  water-  and  gas-free  basis. 
The  crude  material,  when  freshly  sampled  at  the  center  of  the  lake, 
is  composed  of: 

Water  and  gas  volatilized  at  100°  C 29.0  per  cent 

Asphalt  soluble  in  carbon  disulfide 39.0  per  cent 

Asphalt  adsorbed  by  mineral  matter 0.3  per  cent 

Mineral  matter  on  ignition 27 . 1  per  cent 

Water  of  hydration  in  mineral  matter 4.3  per  cent 

Total 99 . 8  per  cent 

Specimens  taken  from  the  various  portions  of  the  lake's  surface, 
after  pulverizing  and  drying  to  constant  weight  in  air  at  room  tem- 
perature, appear  fairly  uniform  in  composition,  averaging: 

Soluble  in  carbon  disulfide 53 .0  to  55  .o  per  cent 

Free  mineral  matter 35. 5  to  37.0  per  cent 

Water  of  hydration,  etc. . ,  * 9,7  per  cent 

The  so-called  "water  of  hydration,  etc."  includes  water  chemi- 
cally combined  with  the  clay,  asphalt  adsorbed  by  the  clay  and  not 
removable  by  carbon  disulfide,  and  the  inorganic  salts  which  are 
volatilized  on  ignition  upon  determining  the  mineral  matter. 

The  mineral  constituents  consist  of  extremely  finely  divided 
silica  and  colloidal  clay,  and  have  the  following  composition : 


IX  SOUTH  AMERICA  187 


SiOs 

70.68- 

66  .  9  pet  cent 

AlaO*  

17.04- 

20  .  9  per  cent 

7.62- 

4  4  per  cent 

CaO  

I 

\  \ 

i  .  o  per  cent 

MgO  

2.46-  1 

i  .  i  per  cent 

K*OandNa2O  

I 

1.22- 

i  .  6  per  cent 

SOt  

O.Q7— 

3  .  8  per  cent 

Cl  

O.22- 

o  .  3  per  cent 

Total 100,00-    100. o  per  cent 

The  mineral  matter  shows  the  following  granularmetric  com- 
position when  separated  into  fractions  by  means  of  air: 

*  Ignited  Ash  Unignited  Mineral 
Residue 

O-IOM v,  . .     37  per  cent  47  per  cent 

io-20/u 1 5  per  cent  1 1  per  cent 

20-30^1 9  per  cent  7  per  cent 

30-40/4 5  per  cent  5  per  cent 

40-50;* 5  per  cent  6  per  cent 

50-60/4 4  per  cent  6  per  cent 

Over  60^ 25  per  cent  18  per  cent 


Total 100  per  cent        100  per  cent 

The  mineral  constituents  of  Trinidad  asphalt  may  be  separated 
by  treating  with  bromoform  (specific  gravity  at  77°  F.  2.59  to 
2.62).  The  lighter  constituents  will  float  to  the  surface  and  the 
heavier  constituents  present,  including  titanite,  zircon,  rutile  and 
glaucophane  will  settle  out.  The  latter  upon  examination  under  the 
microscope  will  disclose  the  characteristic  blue  color  of  glaucophane, 
which  although  not  very  plentiful,  will  aid  in  the  identification  of 
Trinidad  asphalt,  whenever  present  in  a  mixture.26 

The  emulsified  water  contains  mineral  constituents  in  solution 
to  the  extent  of  82.1  grams  (at  110°  C)  per  kilo,  composed  largely 
of  sodium  chloride.  The  gas  is  a  mixture  of  methane,  ethane,  car- 
bon dioxide,  and  nitrogen. 

The  crude  asphalt  is  subjected  to  a  refining  process  by  heating 
it  to  1 60°  C.  to  drive  off  the  water.  A  small  amount  of  volatile 
matter  is  also  removed  during  this  treatment  The  refined  asphalt 
has  been  termed  "parianite."  *7  A  process  has  been  suggested  for 
expelling  the  water,  when  the  asphalt  is  to  be  used  for  constructing 


188  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

pavements,  which  consists  in  mixing  the  crude  asphalt  with  a  suitable 
proportion  of  mineral  aggregate  heated  sufficiently  high  (e.g., 
400°  F.)  to  drive  off  the  water.28  Another  process  consists  in  com- 
minuting the  crude  asphalt,  and  drying  it  at  a  low  temperature  to 
preserve  its  granular  condition.29  The  refined  asphalt  tests  as 
follows : 

(Test    i)    Color  in  mass Black 

(Test   4)    Fracture Conchoidal 

(Test    5)    Lustre Dull 

(Test    6)     Streak Black 

(Test    7)     Specific  gravity  at  77°  F i  .40-1 .42 

(Test    ga )  Hardness,  Moh's  scale i      -2 

(Test    9^)  Penetration  at  115°  F 10      -15 

Penetration  at  77°  F* 1.5-4.0 

Penetration  at  32°  F 0.25-0.75 

(Test   gc)  Consistency  at  115°  F 32.7 

Consistency  at  77°  F 74. 9 

Consistency  at  32,°  F Above  100 

(Test   9</)  Susceptibility  index Greater  than  80 

(Test  10*)  Ductility  (Dow  Method): 

At  115°  F 8.0 

At77°F '. 1.8 

At32°F o.i 

(Test  io£)  Ductility  (Author's  Method): 

At  115°  F 1.5 

At  77°  F i  .o 

At32°F o.o 

(Test  n)    Tensile  strength  (Author's  Method): 

At  115°  F 4.15 

At  77°  F.. 21.0 

At  32°  F 27.0 

(Test  13)    Fraas  breaking-point 57°  F. 

(Test  I  5*)  Fusing-point  (K.  and  S.  method) 188°  F. 

(Test  1 5^)  Fusing-point  (R.  and  B.  method) 206°  F. 

(Teat  15*)  Fusing-point,  pure  asphalt  extracted  from  mineral 

matter  (K.  and  S.  method) 131^°  F. 

(Test  I  $£)  Fusing-point  ditto  (R.  and  B.  method) 149°  F. 

(Test  16)     Volatile  at  335°  F.,  in  5  hrs 1.1-1.7    per  cent 

Volatile  at  409°  F.,  in  5  hrs 4.0-5. 25  per  cent 

(Test  19)    Fixed  carbon 10.8-12.0  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 56-57     per  cent 

Asphalt  retained  by  mineral  matter 0.3          per  cent 

Mineral    matter    on    ignition    with    tricalcium- 

phosphate. , 38 . 5           per  cent 

Water  of  hydra  tion  (clay  and  silica) 4.2           per  cent 

(Testaa)    Carbenes 0.0-1.3    percent 

(Test  23)    Soluble  in  88°  petroleum  naphtha  (pure  asphalt) . .  62-64     per  cent 

(Test  26)    Carbon  (ash-free  basis) 80-82     per  cent 

(Test  27)    Hydrogen  (ash  free  basis) io-n      per  cent 

(Test  18)    Sulfur  (ash-free  basis), 6-8       per  cent 

(Test  29)    Nitrogen  (ash-free  basis) 0.6-0, 8    per  cent 

(Test33)    SoKd  paraffins 1 Trace 


IX 


SOUTH  AMERICA 


189 


(Test  344)  Saturated  hydrocarbons 24.4  per  cent 

(Test  37*0  Saponification  value , 40.0  per  cent 

(Test  380)  Free  asphaltous  acids 6.4  per  cent 

(Test  38^)  Asphaltous  acid  anhydrides 3 . 9  per  cent 

(Test  38*)  Asphaltenes 33.0-37.0  per  cent 

(Test  38^)  Asphaltic  resins 23 ,0-26.  o  per  cent 

(Test  38^?)  Oily  constituents 31.0-32.0  percent 

The  following  more  detailed  tests  have  been  reported:80 


Test 

No. 

Description 

Refined 
Trinidad 

Extracted 
Asphalt 

7 

Specific  gravity  at  77°  F  *  .  *  

1  .4.0 

I   O70 

*d 

Float  test  at  212°  F  

14.02 

A  .t-»/W 

64? 

loa 

Ductility  at  77°  F  

3 

Q 

n 

Fraas  breaking-point  ,  

66°  F. 

<T9°F. 

ita 

Fusing-point  (K..  and  S.  method)  •  

171°  F. 

jy    *•  * 
I4Q°F 

i& 

Fusing-point  (R.  and  B.  method)  

*  /  *   *  • 
203°  F. 

*Ty    c* 
l64°F. 

i$h 

Ubbelohde  drop-point  

270°  F. 

IQOU0  F. 

16 

Volatile  at  325°  F.;   5  hours  

o.o?% 

0.08% 

16 

Loss  (D.I.N.  method)  

1.10% 

1.18% 

lib 

Flash-point  (open-cup)  

460^°  F. 

460^°  F. 

18 

Burning-point  

529°  F. 

529°  F. 

21 

Soluble  in  carbon  disulfide  

58.62% 

99-8<% 

Non-mineral  matter  insoluble  

0.2O 

o  oo 

Mineral  matter  (ash)  ....»..*»»»/  

4I.I8 

0.  1? 

Total  

IOO.OO% 

IOO  OO% 

28 

Sulfur  

4.65% 

f   r0% 

33 

Solid  paraffins: 
Alcohol-ether-fuller's  earth  

O,25% 

0.44% 

Alcohol-ether-sulfuric  acid  

O.40% 

Alcohol-ether-D.LN.  method  

O,28% 

-S7<2 

Acid  value  ...... 

6  o 

O.  J.C 

i8f 

Asphaltenes  

15  1<% 

26   14% 

JUl, 

lid 

Asphaltic  resins  

I7.1<% 

20  .  42% 

i$e 

Oily  constituents  

1  8  .  70% 

11  .  QO% 

Soft  asphalt  constituents  (diff.)  

7-1?% 

12.  C4% 

Total  

58.6<% 

IOO.OO% 

11 

Solid  paraffins  in  oily  constituents  

0.81% 

1.  18% 

Js> 

So-called  Trinidad  uland  asphalt^  represerits  material  which 
overflows  from  the  lake  at  its  edges,  where  it  has  been  exposed  to 
the  action  of  the  weather  for  centuries.  It  is  derived  from  the 
same  source  as  the  lake  asphalt,  and  has  the  same  general  physical 
and  chemical  characteristics*  It  is  known  under  vairious  names ;  for 
example:  ucheese  pitch1'  is  a  variety  which  resembles  the  lake  as-* 


190  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

phalt  most  closely  with  respect  to  its  containing  gas  cavities;  "iron 
pitch"  is  a  variety  which  has  hardened  on  exposure  to  the  weather 
to  such  a  degree  that  it  resembles  refined  lake  asphalt;  "cokey 
pitch"  is  a  variety  which  has  been  coked  or  carbonized  by  brush 
fires,  etc. 

The  land  asphalt  varies  in  its  composition  from  place  to  place, 
but  differs  from  the  lake  asphalt  in  the  following  respects : 

( i^   It  contains  less  gas  and  water  than  the  lake  asphalt 

(2)  It  contains  a  slightly  higher  percentage  of  mineral  matter 
(from  i  to  2  per  cent). 

(3)  More  of  the  volatile  ingredients  have  been  evaporated. 

These  influence  the  tests  as  follows  : 

The  specific  gravity  is  somewhat  higher  (up  to  1.45). 
The  hardness  is  greater. 

The  fusing-point  is  higher  (between  30  and  40°  F.). 
The  volatile  matter  is  less  (about  i  per  cent). 
The  percentage  of  fixed  carbon  is  slightly  higher  (about  2  per 
cent). 

BRAZIL 

State  of  Parana.  Asphalt  occurrences  are  reported  in  many 
localities  in  the  Sierra  da  Baliza,  in  the  crevices  and  pores  of  the 
igneous  rocks.81 

State  of  Sao  Paulo.  Asphalt  is  similarly  reported  in  crevices  of 
a  dyke  at  Fazenda  Saltinho,  in  Rio  Tiete,  9*^  miles  above  Porto 
Martins.82 

ARGENTINA 

Province  of  Jujuy.  An  asphalt  lake,  known  as  the  "Laguna  de 
la  Brea,"  occurs  some  distance  northeast  of  the  City  of  Jujuy.  JThe 
asphalt  is  sulfurous,  of  a  semi-liquid  consistency  which  hardens  at 
the  edges.  It  is  mixed  with  more  or  less  earthy  constituents.  Seep- 
ages of  mineral  oil  are  also  found  locally. 

Province  of  Chubut.  Deposits  of  soft,  impure  asphalt  are 
reported  in  the  village  of  Cornodoro  Rivadavia,  associated  with 
seepages  of  asphaltic  petroleum.  The  asphalt  has  not  been  devel- 
oped, and  no  analyses  are  available. 

Province  of  Mendoza.  Asphalt  deposits,  probably  resulting 
from  seepages  of  petroleum,  occur  in  the  San  Rafael  District  at 
Cerro  de  los  Buitres,  in  the  south  of  Mendoza  Province.33 


IX  EUROPE  191 

COLOMBIA  84 

Department  of  Bolivar.  Numerous  seepages  of  liquid  to  semi- 
liquid  asphalt,  more  or  less  associated  with  mineral  matter,  occur 
along  the  Caribbean  Sea  south  of  Cartagena.  These  were  origi- 
nally reported  by  Humboldt  in  1788,  and  have  been  utilized  largely 
for  calking  ships. 

Department  of  Antioquia.  Numerous  occurrences  of  asphalt 
have  been  reported  between  Nare  and  Puerto  Berrio.35 

Department  of  Santander.  Similar  seepages  of  soft  asphalt, 
mostly  associated  with  sand  and  pebbles,  occur  north  of  the  Soga- 
moso  River  which  empties  into  the  Magdalena  River  south  of 
Puerto  Wilches.  Such  asphalts  have  been  reported  at  Morokoi;  at 
a  brook  called  Puente,  a  few  kilometers  north  of  the  foregoing; 
and  still  another  farther  north,  at  Las  Monas. 

Department  of  Boyaca.  Deposits  of  soft  asphalt  associated 
with  sand  and  clay  are  found  at  Tunja  and  Sogamoso,  north  of 
Bogota,  in  the  Cord  Oriental  mountain  range.  These  have  been 
used  for  paving  the  streets  of  Bogota.  Similar  deposits  have  been 
reported  at  Macheta,  Tuta,  Paipa,  Pesca,  La  Puerta,  Topaga,  Cor- 
rales  and  San  Francisco  in  the  south-central  part  of  this  province. 


36 


ECUADOR 

Province  of  Guayas.  In  the  Santa  Elena  peninsula,  seepages  of 
asphalt  have  been  reported  in  pits  which  have  been  dug  in  pros- 
pecting oil.87 

EUROPE 

FRANCE  8a 

Department  of  Landes,  Near  Bastenne,  about  24  km.  from 
Orthey,  a  moderately  large-sized  deposit  of  asphaltic  sand  is  found, 
associated  with  fossil  shells,  indicating  that  this  asphalt  is  of  animal 
(marine)  origin.  These  shells  are  distributed  throughout  the  as- 
phalt bed,  which  measures  between  10  and  14  ft  thick.  On  expo- 
sure to  the  air,  the  shells  fall  to  pieces  in  a  fine  powder  and  the 
asphalt  hardens  materially,  due  to  the  loss  of  volatile  matter.  An 
analysis  by  Leon  Malo  shows  the  material  to  contain:  asphalt  38.45 
per  cent,  calcium  carbonate  4.9  per  cent,  and  sand  56*59  per  cent. 


192  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

This  deposit  has  been  worked  for  many  years  and  was  used  for 
constructing  the  earliest  asphalt  mastic  pavements.39  Similar  de- 
posits were  formerly  worked  at  Dax. 

Department  of  Gard.  Large  deposits  of  rock  asphalt  have  been 
mined  in  the  Concession  of  St.  Jean-de-Marvejols  since  the  first 
Concession  was  granted  by  a  Royal  Ordinance  on  February  17,  1844. 
Deposits  also  occur  in  the  southern  part  of  this  Department,  includ- 
ing the  Concessions  of  Servas,  Cauvas,  Les  Fumades  and  Puech. 
These  have  long  been  known  (since  1844),  but  are  no  longer 
worked.  Lignite  and  coal  occur  in  the  same  region.  The  asphalt 
is  associated  with  limestone,  sandstone  and  shale,  and  varies  in  per- 
centage between  5  and  16  per  cent  An  average  analysis  shows  it 
to  contain:  asphalt  10  to  12  per  cent,  clay  0.5  to  0.8  per  cent,  cal- 
cium carbonate  84—86  per  cent,  magnesium  carbonate  about  2  per 
cent,  and  moisture  0.5  per  cent  The  penetration  of  the  extracted 
asphalt  runs  as  follows:  at  25°  C.  98,  at  20°  C,  58,  at  15°  C.  32, 
at  10°  C.  20  and  at  5°  C.  10.  At  St.  Jean-du-Gard  it  is  necessary 
to  sink  shafts  1000  ft.  deep  to  reach  the  stratum  of  asphalt,  which 
was  probably  introduced  into  the  limestone  as  an  asphaltic  petro- 
leum, the  lighter  fractions  of  which  evaporated,  leaving  the  asphalt 
behind/0 

Department  of  Haute-Savoie.  Deposits  of  asphalt  associated 
with  limestone  and  sandstone  occur  at  Mussiege,  Frangy,  Lovagny, 
Bourbonges,  and  Chavaroche,  in  strata  between  13  and  16  ft  thick. 
An  analysis  of  the  rock  asphalt  mined  at  Chavaroche  shows  it  to 
contain:  asphalt  29.2  per  cent,  calcium  carbonate  51.6  per  cent,  and 
sand  19,2  per  cent  This  is  used  for  paving  purposes.  The  Lo- 
vagny deposit  contains:  asphalt  4.5  per  cent,  volatile  at  100°  C.  2.3 
per  cent,  and  ash  93.3  per  cent.  The  ash  consists  of  CaCO8  97.60 
per  cent,  MgCOa  0.44  per  cent,  CaSO4  0.48  per  cent,  Fe5Os  0.62 
per  cent,  and  A12O3  0.82  per  cent41 

Department  of  Ain.  The  asphalt  dejposits  extend  across  the 
boundary  line,  separating  the  Departments  of  Haute-Savoie  and 
Ain,  ranging  in  a  northeasterly  direction,  and  culminating  in  the 
ISFeuchatel  (Swiss)  region  in  the  north.  At  Bellegarde,  in  the  north- 
eastern part  of  the  Department,  occurs  a  deposit  of  asphaltic  lime- 
stone, unevenly  impregnated  with  asphalt,  and  associated  in  part 
heavy  petroleum  oils*  The  well-known  Seyssel  deposit  also 


IX 


EUROPE 


193 


occurs  in  this  Department,  at  Pyrimont42  Minor  deposits  occur 
also  at  Volant,  Belley,  Challenges,  Forens,  Obagnoux,  Corbonod, 
Confort,  etc.,  consisting  of  a  fine-grained  limestone  impregnated 
with  asphalt.  This  region  is  illustrated  in  Fig.  61.  The  deposits 
consist  of  a  series  of  hillside  quarries  on  both  banks  of  the  Rhone 


Bllllat 


* 

«* 


I 
Q 


Bcyrlat 


L'hoprtal 


•Chancy 


FIG.  61. — Map  of  Seyssel  Asphalt  Deposit,  France. 

River.  The  asphalt  impregnation  varies  from  2  to  8  per  cent  as  a 
maximum,  the  balance  consisting  almost  exclusively  of  calcium  car- 
bonate. Fossil  shells,  also  crystalline  calcite,  are  frequently  encoun* 
tered.  The  deposits  at  Pyrimont  have  been  worked  for  many  years 
by  a  series  of  underground  tunnels,  in  eight  beds,  varying  in  •thick*. 


194 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


ness  from  2  to  5  meters,  on  the  eastern  bank  of  the  Rhone  River. 
Three  grades  of  asphalt  have  been  produced,  containing  3  per  cent, 
5-6  per  cent,  and  8  per  cent  of  asphalt  respectively.  The  chief 
merit  of  this  product  lies  in  the  intimacy  of  its  impregnation  with 
asphalt,  and  the  fine  granular  structure  of  the  associated  calcium 
carbonate.  Prior  to  1914  from  5000  to  20,000  tons  were  mined 
annually.  The  following  analysis  represents  the  average  composi- 
tion of  the  Seyssel  product: 

Water  ...........................................  i-9  -  °-°    percent 

Asphalt  (fusing-point,  87°  R,  K.  and  S.  method)  ......  8.00-  8.  15  per  cent 

Magnesium  carbonate  ..............................  o.  10            per  cent 

Calcium  carbonate  ....  ............................  89  .  55~9i  -  30  per  cent 

Iron  and  aluminium  oxides.  .........................  0.15             P61"  cent 

Insoluble  in  acid  ..................................  o.  10-  0.45  per  cent 

^  etc  ..........................................  o.  io-  o.  20  per  cent 


The  extracted  asphalt  shows  the  following  penetrations  (Test 
gb)  :  at  77°  F.  too  soft;  at  60°  F.  136;  at  50°  F.  76;  at  40°  F.  40. 

Fig.  6  1  shows  the  location  and  extent  of  the  Seyssel  deposit. 
Occurrences  of  asphalt  have  also  been  reported  at  Lelex  and 
Chezery,  in  the  valley  of  the  Valserine,  north  of  Bellegarde. 

Department  of  Basses-Alpes.  Two  deposits  have  been  de- 
scribed in  the  vicinity  of  Forcalquier,  one  (A)  associated  with  lime- 
stone and  the  other  (B)  with  a  siliceous  base,  testing  as  follows:  43 


SiOa 

CaCOs 

Fe2O8andAl2O8 

H20  and  Loss 

Asphalt 

«  *  »> 

f\      *   »   *  . 

"B"  

Trace  to  0.54% 
58.34-59.13% 

90.63-80.58% 
31.34-28.40% 

0.01-0.80% 
0.56-0.93% 

o.i3"3-52% 
1.31-0.27% 

9.33-14.50% 
8.45-11.27% 

Department  of  Puy-de-D6me  (Auvergne).  Rock  asphalt  de^ 
posits  occur  in  numerous  localities.  The  only  present  source  of 
production  is  at  Pont-du-Chateau  (also  at  Chamalieres,  near  Cler* 
mont-Ferr and),. where  12,000  to  20,000  tons  of  rock  asphalt  com- 
posed of  n.o  per  cent  asphalt  associated  with  SiO2  (suitable  for 
an  acid-resisting  mastic)  are  produced  annually.  Limited  opera- 
tions have  been  carried  on  at  various  times  in  the  past  at  Lussat, 
Malintrat,  Gites-des-Roys,  Puy-de-Croville,  du  Cortal,  Pontgibaud 
(west  of  the  Chain  of  Puys),  Plain  of  Limagne,  and  other  minor 
localities." 


IX 


EUROPE 


195 


Department  of  Haute  Vienne.  Minor  occurrences  have  been 
reported  at  Limoges,  in  quartz  veins  traversing  gneiss. 

SWITZERLAND 

Extensive  deposits  of  asphalt-impregnated  limestone  occur  west 
of  Neuchatel  Lake,  in  the  so-called  Val  de  Travers  region.  These 
have  been  exploited  for  many  years  and  marketed  under  the  names 


FIG.  6a.— Neuchatel  and  Val  de  Travers  Asphalt  Deposits. 

"Neuchatel  Asphalt"  and  "Val  de  Travers  Asphalt."  45  The  exact 
location  of  the  region  is  shown  in  Fig.  62,  The  percentage  of  as- 
phalt varies  considerably;  thus,  the  "ordinary"  grade  contains  8~~io 
per  cent  of  asphalt,  the  so-called  "rich"  grade  contains  10-12  per 
cent  of  asphalt. 

The  average  product  contains:  asphalt  10.15  per  cent  (fusing- 
point  50°  F.,  K.  and  S.  method),  calcium  carbonate  88.4  per  cent, 


106 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


calcium  sulfate  0.25  per  ceiit,  iron  and  aluminium  Oxides  0.25  per 
cent,  magnesium  carbonate  0.3  per  cent,  matter  insoluble  in  acid 
0.45  per  cent,  and  loss  0.5  per  cent  The  extracted  asphalt  shows 
the  following  penetrations  (Test  $b)  :  at  77°  F.  too  soft;  at  60°  F. 
1 12;  at  50°  F.  57.  The  fusing-point  (Test  15^)  is  43°  C,  and  the 
ductility  at  77°  F;  (Test  100)  over  115  cm. 

The  theory  has  been  advanced  that  these  asphalts  have  been 
produced  by  the  decomposition  of  marine  animal  and  vegetable 
matters,  which  is  borne  out  by  the  associated  fossils. 

Outcrops  occur  at  Auvernier,  Bevaix,  Bois-de-Croix,  Presta, 
Bulles,  and  St.  Aubin,  south  of  Neuchatel,  on  the  western  shore  of 
Lake  Neuchatel,  carrying  smaller  percentages  of  asphalt  than  the 
preceding. 

ALSACE-LORRAINE 

The  deposits  in  this  region  occur  in  a  well-defined  area  in  the 
neighborhood  of  Lobsann  a  short  distance  north  of  Strasbourg,  as 
shown  in  Fig.  63.  The  asphalt  strata  have  been  traced  6  to  7  miles 


Schacht  Pechelbronn 

*         SOULTZ-SOUS-FOR 
Walbourg  • 


FIG.  63,— Map  of  Lobsann  Asphalt  Region,  Alsace-Lorraine, 


extending  through  Soultz-sous-Forets,  Pechelbronn  and  Lamperts- 
loch.46  They  occur  as  asphalt-impregnated  limestone  and  sandstone 
associated  with  lignite.  Petroleum  is  also  found  locally.  The  asphalt 
strata  average  about  80  ft.  in  thickness  and  carry  many  fossils.  The 


IX  EUROPE  197 

region  is  badly  faulted.    The  bituminous  limestone  has  the  following 
average  composition: 

Asphalt  (fusing-poin t  77°  F.,  K.  and  S.  method) 1 1 . 9  -i  2 . 32  per  cent 

Calcium  carbonate 69.0  -71 .43  per  cent 

Iron  and  aluminium  oxides 4.3  -  5.9   per  cent 

Sulfur 5.0-5.6   per  cent 

Magnesium  carbonate 0.3               per  cent 

Silica 3  *  *  5~  3-65  per  cent 

Loss,  etc * 1.7  -  3.4   per  cent 

The  asphaltic  sandstone  at  Pechelbronn  occurs  in  veins  3  to  6  ft. 
thick,  containing  15—18  per  cent  of  a  soft,  viscous  asphalt  associated 
with  82-85  per  cent  of  sand.  The  asphalt  when  extracted  shows  a 
gravity  between  0.90  and  0.97  at  77°  F.  Large  quantities  of  as- 
phalt have  been  mined  in  this  region  for  paving  purposes, 

SPAIN 

Burgos  Province.  At  Maesta  there  has  been  reported  an  as- 
phalt deposit  containing:  8.80  per  cent  asphalt,  68.75  per  cent  SiO2, 
9.15  per  cent  CaCO3,  8.10  per  cent  MgCO3,  4.35  per  cent  Fe3O3 
and  Al2Oa,  and  0.85  per  cent  water  and  loss. 

GERMANY  47 

Province  of  Hanover.  At  Limmer,  a  small  village  near  Ahlem 
in  the  plains  of  Acker,  about  18  miles  west  of  Hanover  there  occurs 
a  deposit  of  asphaltic  limestone  measuring  1600  by  2250  ft.  which 
was  discovered  by  Dr.  Eirinis  d'Eyrinys  about  1730  and  first  mined 
in  1843  by  D.  H.  Hennig.48  The  rock  carries  between  8  and  20 
per  cent  of  asphalt  and  contains  numerous  fossil  shells.  As  freshly 
mined  it  has  a  brownish  to  gray-brown  color,  and  the  asphalt  im- 
pregnation is  very  soft  in  consistency  containing  a  large  proportion 
of  volatile  constituents.  The  average  analysis  shows: 

Asphalt 8 . 3  per  cent 

Calcium  carbonate 56 . 5  per  cent 

Magnesium  carbonate , 27 .  o  per  cent 

Iron  and  aluminium  oxides 8.2  per  cent 

Total 100. o  per  cent 

The  richer  portions  of  the  vein  test  as  follows : 

Asphalt  (fusing-point  61°  F.s  K.  and  S.  method) 13.4-14.3  per  cent 

Calcium  and  magnesium  carbonates 67  per  cent 

Iron  and  aluminum  oxides,  etc 17-  5~J9* 5  Per  cent 

t ...,., * 0.3-  1.18  per  cent 


198 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


At  Waltersberge,  near  Limrner,  a  very  large  deposit  of  asphaltic 
limestone  is  found,  containing  5  to  7  per  cent  of  asphalt*  It  is  esti- 
mated that  about  3,000,000  tons  occur  in  this  deposit,  but  the  ma- 
terial is  so  poor  in  asphalt  that  it  must  be  enriched  before  it  can  be 
used  for  paving  purposes,  although  it  has  not  given  good  results  as 
such,  on  account  of  the  large  percentage  of  clay  present 


/,-/;//'; 

'"  t  f  A'-1 

W%     f'7' 


10     0     10    20    30   40m. 

i..,,.,.,,! ^ ^^^^ 

1  :  1500 
FIG.  64. — Herzog  Wilhelm  Mine  at  Holzen,  Germany. 

In  the  District  of  Holzminden,  in  the  Dukedom  of  Braun- 
schweig, a  short  distance  west  of  the  village  of  Holzen,  on  the  west 
bank  of  the  River  Ith,  there  occurs  one  of  the  most  productive  de- 
posits in  Germany,  which  has  been  identified  with  the  neighboring 
towns  of  Eschershausen  and  Verwohle,49  discovered  in  1601  by 
woodsmen,  who  first  utilized  the  substances  as  fuel.  This  includes 
the  uHerzog  Wilhelm"  mine,  the  uAugusta  Victoria,"  "Verwohle," 
"Greitbergbruch,"  "Wintjenberg"  and  "Stolln  Gustav"  quarries, 
the  first  two  of  which  are  illustrated  in  Figs*  64  and  65.  A  plan  of 
the  entire  region  is  shown  in  Fig.  66.  The  deposits  consist  of  as- 


IX  EUROPE  199 

phaltic  limestone,  containing  10  per  cent  asphalt  at  the  top,  which 
gradually  diminishes  to  3  per  cent  at  the  lower  levels,  averaging  6 
to  8  per  cent,  and  characterized  by  the  presence  of  fish  scales. 

The  asphalt  stratum  has  been  traced  for  approximately  14,500 
ft.  and  forms  a  succession  of  layers  65  ft  thick  carrying  a  variable 


FIG.  65. — Augusta  Victoria  Quarry  at  Holzen,  Germany. 

percentage  of  asphalt  associated  with  limestone,  and  separated  by 
clay  and  shale.    The  average  asphalt  analyzes  as  follows : 

Asphalt  (fusing-point  65°-7o°  F.,  K.  and  S.  method) ...  5-4  -  8 .  J    per  cent 

Calcium  carbonate 80.0  -90.9    per  cent 

Iron  and  aluminium  oxides 4.0-5.0   per  cent 

Silica 2. 55-  4-77  P^  cent 

Loss o.  15-  a .  ii  per  cent 

The  Verwohle  rock  asphalt  shows  the  following  average  com- 
position : 

(Test   7)    Specific  gravity  at  77°  F 2.326 

Voids 2.8    per  cent 

(Test  21)    Soluble  in  carbon  disulfide 7  -.73  Per  cent 

Non-mineral  matter  insoluble o .  60  per  cent 

Mineral  matter 9*  -67  per  cent 


200 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


DC 


Legend. 

Deutsche  Asphalt  Ahtien  GeseUsckaft  (Eschershausen). 
Hannoversckt  Baugesettschaft  Akt.  Ges.  (Hannover}. 
Indus tr it gesellschaf t  G.  m.  b.  UJttr  Steine  u.  Erden.  (Etcher shavsen). 
VorwoUer  Asphalt  Co.  Limited  (Eschershauscn). 
Union  Co. 

Vorwohkr  Asphalt  Fabrik  L.  Hoarmnn  u.  Co.  G.  m.  6.  JET. 
Asphdt  Con-panic  Limited. 
Tkomae. 

Herkulcs  Gcwerkschaft* 
Bits  Kalkwrk. 


FiG.  66. — Verwohle  and  Escherahausen  Asphalt  Deposits,  Germany. 


IX  EUROPE  201 

The  extracted  asphalt  tests  as  follows: 

(Test  7)    Specific  gravity  at  77°  Ff 1 .019 

(Test   9^)  Penetration  at  77°  F 95 

(Test  13)    Fraas  breaking-point Below  20°  C. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 47°  C. 

(Test  15^)  Ubbelohde  drop-point 57°  C. 

(Test  28)    Sulfur i .  67  per  cent 

This  material  must  be  enriched  by  the  addition  of  Trinidad, 
Limmer,  or  petroleum  asphalt,  before  it  becomes  suitable  for  con- 
structing pavements.  It  is  marketed  in  three  forms,  viz. : 

1 I )  Mastic  cake,  which  is  prepared  by  first  grinding  the  rock 
asphalt  to  a  powder,  which  is  heated  to  180-200°  C.  for  4-6  hours, 
whereupon  sufficient  asphalt  is  added  to  enrich  same  to  14-16  per 
cent,  and  finally  cast  into  the  form  of  cakes,  suitable  for  use  in 
mastic  work. 

(2)  Powder,  which  is  prepared  by  heating  the  ground  rock 
asphalt  in  steam-jacketed  kettles  to  80°  C.  with  an  "enricher"  and 
under  strong  agitation,  until  it  forms  so-called  "clinker"  containing 
about  1 1  per  cent  asphalt,  which  in  turn  is  cooled  and  ground  to  a 
powder,  suitable  for  use  under  compression  to  form  sheet-asphalt 
pavements. 

(3)  Asphalt-tiles,  which  are  made  by  heating  the  ground  rock 
asphalt  and  compressing  same  into  plates  28  by  25  cm.  and  1.5  to 
6.0  cm.  thick  by  means  of  hydraulic  presses  operating  at  180  to  400 
atmospheres.     The  resulting  tiles  are  used  for  surfacing  factory 
floors,  bridges,  viaducts,  etc. 

A  small  deposit  has  been  reported  at  Wintjenberg  in  this  same 
neighborhood,  but  has  not  been  worked  to  any  extent. 

Province  of  Westphalia.  Minor  deposits  have  been  found  near 
the  villages  of  Darfeld,  Buldern,  Hangenau,  and  Appelhiilsen,  asso- 
ciated with  clay  and  shale. 

Province  of  Hessen.  At  Mettenheim 50  between  Worms  and 
Appenheim,  occurs  a  deposit  of  asphaltic  limestone  and  clay  carry- 
ing a  large  quantity  of  fossil  fish  remains.  The  rock  contains  be- 
tween 74.4  and  82.6  per  cent  of  asphalt  of  a  comparatively  high 
fusing-point. 

Province  of  Baden.  Minor  occurrences  have  been  reported 
near  Dossenheim,  north  of  Heidelberg,51  also  near  Ottenau,  north- 
east of  Baden-Baden.52 


202 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


Province  of  Silesia.  Asphalt  has  been  found  in  the  granite  of 
Striegau  and  in  the  northern  part  of  the  Black  Forest,  associated 
with  calcite  and  hematite,53 

JUGOSLAVIA 

Province  of  Dalmatia.54  A  deposit  of  asphaltic  limestone  occurs 
at  Vrgorac,  having  a  specific  gravity  at  77°  F.  of  1.697  containing 
an  average  of  26  per  cent  of  asphalt.  Analyses  show  the  following 
ingredients : 


Analysis  I, 
Per  Cent 

Analysis  2, 
Per  Cent 

Analysis  3, 
Per  Cent 

Asphalt  

2.94 

7.12 

38.92 

Silica.   ...                 .                  

21  .70 

Iron  and  aluminium  oxides 

7    12 

<8.  10 

Iron  carbonate                                

I  .  IO 

Calcium  carbonate  

l6.6o 

61.08 

Magnesium  carbonate     

12.  C8 

Sodium  chloride 

O.  07 

Water  

4.  10 

Total  

lOO.OO 

99.87 

IOO.OO 

The  first  analysis  represents  an  asphaltic  limestone,  containing 
silica,  the  second  analysis  represents  an  asphaltic  shale,  and  the 
third  an  asphaltic  limestone  (pure) .  Considerable  asphalt  has  been 
derived  from  this  deposit  for  paving  purposes. 

Asphaltic  shales  have  been  reported  near  the  town  of  Skrip,  on 
the  Island  of  Brazza,  situated  about  I  mile  from  the  mainland,  in 
the  Adriatic  Sea,  containing  between  5  and  40  per  cent  of  soft  as- 
phalt, analyzing  as  follows:  asphalt  7.1  per  cent,  calcium  carbonate 
58.1  per  cent,  calcium  sulfate  32.6  per  cent,  silica  2.1  per  cent,  and 
undetermined  o.  i  per  cent.  The  layers  are  between  2  and  4  ft.  in 
thickness.  There  also  occurs  a  deposit  of  asphaltic  limestone  con- 
taining about  13  per  cent  of  asphalt  and  87  per  cent  of  calcium 
carbonate,  having  a  brownish-black  color  and  containing  a  substan- 
tial proportion  of  volatile  matter. 

At  Morowitza  near  Sebenico,  on  the  Adriatic  Sea,  occurs  a 
deposit  of  asphaltic  limestone  carrying  10  to  15  per  cent  of  asphalt, 
95  per  cent  of  calcium  carbonate,  and  about  4  per  cent  of  mag- 
nesium carbonate. 


IX  EUROPE  203 

At  Porto  Mandorlo,  near  the  town  of  Trau  on  the  Adriatic  Sea, 
occur  beds  of  crystalline  limestone  of  a  brownish  color  containing 
9.2  per  cent  of  asphalt  and  90.8  per  cent  of  calcium  carbonate. 
Further  deposits  have  been  located  in  this  region  at  Biskupija  and 
Vinjisce,  also  at  Suhidol,  Bua  and  Dernis-Knin. 

Province  of  Herzegovina.55  A  deposit  of  asphaltic  limestone 
occurs  at  the  village  of  Popovo  Polje,  having  a  black  to  grayish- 
black  color,  and  carrying  between  1 6  to  20  per  cent  of  asphalt  It 
contains  a  large  percentage  of  volatile  matter,  which  causes  the 
crude  material  to  ignite  very  readily  and  burn  with  a  luminous  flame. 

A  little  south  of  the  village  of  Misljan,  and  east  of,  the  town  of 
Popovo  Polje,  occurs  another  and  larger  deposit  of  asphaltic  lime- 
stone 6  to  20  ft.  thick.  The  asphaltic  impregnation  is  sticky  and 
semi-liquid,  varying  between  3  and  35  per  cent  The  richer  varieties 
ignite  readily  and  burn  with  a  luminous,  smoky  flame. 

A  deposit  of  asphaltic  limestone  about  100  ft  wide  and  10  ft. 
thick  occurs  at  Dracevo,  about  2  }/2  miles  east  of  the  city  of  Met- 
kovic.  The  rock  is  of  a  brownish  black  to  dull  black  color,  carrying 
5.4  per  cent  of  asphalt  It  is  not  rich  enough  to  be  worked 
profitably. 

Province  of  Styria  (Steiermark).  Traces  have  been  found  at 
Trenchtling,  northeast  of  Trofaiach,  and  in  the  neighborhood  of 
Messnerin.56 

AUSTRIA 

Province  of  Tyrol.57  A  very  peculiar  asphaltic  shale  occurs  at 
See f eld,  5000  ft.  above  the  sea-level,  in  beds  several  feet  thick  with 
numerous  fossil  fish  remains,  in  between  layers  of  dolomite.  This 
deposit  constitutes  one  of  the  main  sources  of  supply  of  ichthyol, 
which  is  recovered  upon  subjecting  the  material  to  a  process  of 
destructive  distillation  in  suitable  retorts.  The  material  best  suited 
for  this  purpose  is  composed  of  the  following: 

Asphalt 26,41  per  cent 

*   Calcium  and  magnesium  carbonates 38 . 22  per  cent 

Clay 6.67  per  cent 

Silica *  9 . 03  per  cent 

Iron  oxide 5, 95  per  cent 

Loss  and  moisture 3-7^  per  cent 

Total loo.oo  per  cent 


204  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  DC 

HUNGARY  5S 

Province  of  Bihar.  Deposits  occur  at  Tataros,  Derna  and 
Bodonos,  located  east  and  northeast  of  the  town  of  Nagy-Varad 
(Grosswardein),  between  the  Sebes  Koros  and  Berettyo  Rivers. 
The  Tataros  deposit  consists  of  sand  containing  a  soft,  sticky  as- 
phalt with  a  characteristic,  penetrating  odor,  which  has  been  ex- 
ploited under  the  name  uDerna  Asphalt.''  It  i$  associated  with  a 
consolidated  sandstone  in  strata  between  6  and  25  ft  thick,  5000 
ft.  long  and  4000  ft.  wide.  Large  quantities  of  asphalt  have  been 
mined  from  this  deposit,  which  constitutes  one  of  the  largest  sources 
of  supply  iniiungary.  Analysis  shows  between  15  and  22  per  cent 
asphalt,  fusing  at  83°  F.  (K.  and  S.  method).  The  water-extrac- 
tion process  has  been  used  to  separate  a  semi-liquid  asphalt  from 
the  sand,  leaving  a  residue  containing  3  per  cent  of  asphalt  which 
could  not  be  separated.  The  pure,  soft  asphalt  thus  separated  is 
distilled  to  recover  the  heavy  oils  and  the  residue,  comprising  about 
44  per  cent  of  the  extracted  asphalt,  is  converted  into  mastic  by 
mixing  with  limestone.  The  product  has  been  used  with  success  for 
paving  the  streets  of  Budapest.  During  the  World  War,  the  puri- 
fied asphalt  was  shipped  to  Germany  and  used  in  the  manufacture 
of  rubber  goods. 

A  short  distance  east  of  Felso  Derna  there  occurs  a  bed  of  sand 
asphalt,  very  similar  in  character  and  composition  to  that  found  at 
Tataros,  carrying  15  to  22  per  cent  of  asphalt.  The  extracted  as- 
phalt contains  0.73  per  cent  of  sulfur,  5.4  per  cent  of  ash,  and  1.6 
per  cent  of  crystallizable  paraffin/9 

CZECHOSLOVAKIA 

Province  of  Trecsen.  At  Strecno,  on  the  River  Waag,  near 
Zsolna  (Sillein),  at  the  foot  of  the  Lipovec  Mountains,  there  occurs 
a  deposit  of  dolomitic  limestone  containing  6.0  per  cent  asphalt,60 
fusing  at  37°  C.  (K.  and  S.  method) .  The  asphalt  contains  asphal- 
tic  acids  1.37  per  cent,  asphaltenes  2.11  per  cent,  asphaltic  resins 
41.29  per  cent,  and  oily  constituents  51.25  per  cent.61 

Provinces  of  Moravia  and  Silesia.  Occurrences  of  rock  asphalt 
have  been  reported  at  Malenowitz  and  Zin  (northeast  of  Napa- 
gedl),  Palkowitz,  Chlebowitz  (near  Friedek),  Wiseck  (near  Letto- 
witz),etc. 


IX 


EUROPE 


205 


RUMANIA 

At  Matitza,  on  both  sides  of  the  Matitza  River,  there  occurs  a 
large  deposit  in  veins  30  to  40  m.  thick.  It  is  brittle  at  ordinary 
temperatures,  has  a  dull,  dark  color,  and  a  characteristic  odor.  The 
material  contains  25  to  33  per  cent  asphalt,  having  a  specific  gravity 
of  1.07  to  1.09  at  77°  F.,  and  a  fusing-point  of  41°  C.  (K.  and  S. 
method).  An  average  analysis  shows:  water  4.36  per  cent,  asphalt 
30.23  per  cent,  silica  41.10  per  cent,  iron  and  aluminium  oxides 
1 8.08  per  cent,  calcium  carbonate  4.43  per  cent,  and  the  balance 
sodium  and  potassium  salts.  Large  quantities  of  paraffin  wax  are 
produced  upon  distillation.62 

ALBANIA 

Selenitza  (Selinitea).  A  fairly  extensive  vein  of  hard  asphalt 
in  lenticular  form  occurs  at  Selenitza,  25  km.  west  of  Valona 
(Avlona),  near  the  junction  of  the  Vojutza  (Vojusa)  and  Sauchista 
Rivers,  close  to  the  railway  line.  This  deposit  was  first  mentioned 
by  Aristotle  (384-322  B.C.),  and  subsequently  described  in  detail 
by  the  Roman  writer  Aelianus  Claudius  (Aelian),  about  100  A.D.88 
It  has  been  used  for  paving  compositions,  for  manufacturing  paints 
and  composition  roofings.  Between  4000  and  6000  tons  are  pro- 
duced annually.  It  is  on  the  border  line  between  true  asphalts  and 
"glance  pitch,"  and  tests  as  follows:64 


Test 

No. 

Description 

Refined 
S616nitza 

Extracted 
Asphalt 

i 

Color  in  mass  

Glossy  black 

Glossy  black 

Fracture  

Conchoid  al 

Conchoid  al 

6 

Streak  

Black 

Black 

Specific  gravity  at  77°  F  

1.21 

1  .080 

<& 

Penetration  at  77°  F  ,  

O 

o 

ioa 

Ductility  at  77°  F  

o 

o 

i  ^ 

Fraas  breaking-point  

>77°F. 

>77°F. 

I  C/2 

Fusing-point  (K.  and  S.  method)  -  *  

210°  F. 

217°  F. 

*  j** 
ic£ 

Fusing-point  (R.  and  B.  method)  

264°  F. 

*o  l    *  • 

2$iM9  F, 

*  jv 

I  eh 

Ubbelohde  drop-point  *  .  .  .  ,  

284°  F. 

20C°F. 

*jf* 

16 

Volatile  at  325°  F.,  5  hrs  

0.0% 

0.0% 

Loss  (D.I.N.  method)  

0.6% 

0.7% 

nb 

Flash-point  (open-cup)  

566^°  F. 

?6c°  F. 

18 

Burning-point  r  «,..,.  

628°  F. 

6280?F* 

21 

Soluble  in  carbon  disulfide  .  ,  ,  ,  

84.62% 

QQ  .  86% 

Non-mineral  matter  insoluble  ,  , 

0,20% 

yy  •  uv  /Q 
o.00% 

Mineral  matter  (ash)  

I<M8% 

O.I4% 

Total  

100,00% 

IO6.  00% 

206 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


Test 
No. 

Description 

Refined 
S&gnitza 

Extracted 
Asphalt 

18 

Sulfur  

6.2C% 

7.4.0% 

33 

Solid  paraffins: 
Alcohol-ether-fullers1  earth  

O    <Q% 

0.70% 

Alcohol-ether-sulfuric  acid  

o.  ?8% 

Alcohol-ether-D.I.N.  method  

0.4.0% 

Tja 

Acid  value  

^•35 

2.QO 

3$c 

Asphaltenes  

18  20% 

AC   2O% 

l&d 

Asphaltic  resins     

I<   QO% 

1  8  80% 

JWt* 
38* 

Oily  constituents  .  ,  ,  

20  .  70% 

2A  .  CO% 

Soft  asphalt!  c  constituents  

Q  72% 

II    CO% 

Total  

84.52% 

100.00% 

11 

Solid  paraffins  in  oily  constituents  

1.72% 

2.01% 

ITALY  65 

The  general  location  of  the  asphalt  deposits  in  Italy  are  shown 
in  the  map  illustrated  in  Fig.  67. 

Compartment  of  Marches. 

Province  of  Pesaro  ed  Urbino.  Impure,  solid  asphalt  is  found 
at  Sant'  Agata  Feltria  associated  with  sulfur,  but  is  not  mined  ac- 
tively. At  Tallamello  and  Urbino,  deposits  of  solid  and  semi-liquid 
asphalt  occur  associated  with  more  or  less  sulfur.  These  are  of  no 
commercial  importance,  but  are  of  interest  merely  from  a  geological 
standpoint 

Compartment  of  Abruzzi  e  Molise. 

Province  of  Chieti.  In  the  neighborhood  of  San  Valentino, 
extensive  deposits  of  asphaltic  limestone  have  been  worked  in  strata 
2,1/2  to  3  miles  long  and  about  100  ft.  thick.  Quarries  have  been 
opened  up  in  the  Valley  of  the  Pescara  River  at  the  villages  of 
Roccamorice,  Abateggio,  Manopello,  Lettomanopello,  Tocco,  and 
Papoli.  Three  distinct  zones  are  distinguished.  The  lower  carries 
between  9  and  10  per  cent  of  asphalt,  the  middle  an  average  of  17 
per  cent,  and  the  upper  9  to  30  per  cent  In  certain  localities  the 
asphalt  has  a  rubbery  consistency,  and  is  deep  black  in  color,  and  in 


IX 


EUROPE 


207 


®  ASPHALT  DEPOSITS 


FIG.  67. — Map  of  Italian  Asphalt  Deposits. 


208 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


others  it  is  very  soft  and  semi-liquid.    The  deposits  are  rich  in  fossil 
shells.    Analyses  show  the  following  composition : 66 


San 
Spin  to, 

Per  Cent 

Piano 
dei 
Monaci, 
Per  Cent 

Cusano, 
Per  Cent 

San 
Giorgio, 

Per  Cent 

Acqua- 
fredda, 

Per  Cent 

Fonti- 
celle, 

Per  Cent 

Letto- 
mano- 
pello, 
Per  Cent 

Rocca- 

morice, 

Per  Cent 

Moisture  

0.64 

10.72 
82.25 
5.50 

0.40 
11.70 
62,23 
24.80 

0.98 
15.70 
49.70 
32.00 

0.46 
12.06 

85-30 
i  .40 

0.66 
10.62 
86.40 
1.50 

O.22 
10.96 

86.00 

I  .20 

Asphalt  

7.15 
73-76 
14.26 
1.72 
3.02 
o.n 

12.46 
77-53 
4-71 
2.63 
2.17 
0.50 

CaCOj  

MgCOi  

CaSO4  

Clay  

0.74 
0.15 

0-37 
0.06 

0.44 

0.32 
0.42 
0.82 

0.16 
0.42 

0.20 

0,52 
0.30 

1.18 
0.32 

SiOi  

These  deposits  are  especially  suited  for  pavements  in  tropical 
climates  and  have  been  used  with  good  results  in  Cairo,  Bombay, 
Rio  de  Janeiro,  etc.  A  number  of  mines  have  been  opened  up  along 
this  valley  amidst  precipitous  mountains  attaining  elevations  up  to 
10,000  ft.  The  rock  asphalt  is  transported  by  aerial  ropeway  and 
narrow  gauge  surface  tracks  and  the  development  has  been  effected 
in  the  face  of  great  natural  difficulties. 

Compartment  of  Calabria 

Province  of  Baslllcata  (Potenza).  Asphaltic  limestone  pros- 
pects have  been  reported  at  Tamutola,  Magliano  Setere  and 
Leviano. 

Compartment  of  Campania 

Province  Terra  dl  Lavoro  (Caserta).  One  of  the  largest  as- 
phalt quarries  in  the  entire  region,  which,  however,  has  not  been 
very  active  in  recent  years,  occurs  at  Colle  San  Magno.  Analyses 
of  the  product  as  mined  show  it  to  be  composed  of  the  following : 

Asphalt 7. 15  per  cent 

Calcium  carbonate 73 , 76  per  cent 

Calcium  sulfate i .  72  per  cent 

Iron  and  aluminium  oxides 3 .02  per  cent 

Magnesium  carbonate* 14. 24  per  cent 

Silica, o.  10  per  cent 

Prospects  of  asphaltic  limestone  occur, at  Liri,  Frosione,  Monte 
San  Giovanni,  Banco,  Castro  dei  Volsci,  Filletino  and  Collepardo. 


IX  EUROPE  209 

Compartment  of  Sicily 

Province  of  Syracuse*7  The  largest  and  most  important  Italian 
asphalt  deposit  occurs  at  Ragusa,  about  8  miles  from  the  southern 
coast  of  Sicily,  on  the  River  Irminio,  in  a  bed  10  to  50  ft  thick  and 
1600  to  2000  ft.  long.  It  was  discovered  in  1838  and  first  utilized 
for  building  stone,  and  later,  about  1856,  exploited  for  compressed 
asphalt  work.  Fig.  68  shows  a  general  view  of  the  principal  mine, 
Fig.  69  illustrates  the  tunnelling  operations,  and  Fig.  70  shows  the 
rock  asphalt  sawn  into  blocks  and  slabs  as  it  is  blasted  from  the 
deposit.  The  rock  contains  variable  percentages  of  asphalt,  ranging 


nu  05. — /ispnait  mine  at  Kagusa,  Italy. 


from  2  to  30  per  cent,  associated  with  a  soft  consolidated  limestone 
composed  largely  of  fossil  shell  remains.  Several  grades  of  rock 
asphalt  are  mined,  including  a  brown  variety  relatively  poor  in 
asphalt,  carrying  between  3  and  7  per  cent,  also  a  black  variety 
carrying  about  15  per  cent.  Commercial  grades  usually  contain  6 
to  10  per  cent,  and  occasional  pockets  are  encountered  running  as 
high  as  12  to  1 8  per  cent.  The  rock  containing  6  to  9  per  cent  is 
marketed  for  use  as  mastic,  and  the  leaner  varieties  containing  an 
average  of  3  per  cent  of  asphalt  are  distilled  in  retorts  to  recover 
the  oils.  In  1924,  there  were  16  furnaces  in  operation,  yielding 
30,000  tons  of  distillate  per  annum.  The  retorts  are  arranged  in 
groups  of  four.  Each  oven  is  15.5  meters  high  and  of  rectangular 


210 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


cross  section.  The  waste  gases  are  used  to  promote  combustion  of 
the  rock.  The  maximum  temperature  is  about  730°  C.  and  the 
distillation  zone  ranges  from  200  to  600°  C.  The  distillate  is 
practically  free  from  paraffin  and  contains  up  to  2  per  cent  phenols. 
It  compares  with  crude  petroleum  of  Ohio  and  Texas  origin.  To 


FIG.  69. — Tunnelling  Operations  at  Ragusa  Mine. 

obtain  I  ton  of  distillate,  1 8  to  20  tons  of  asphaltic  rock  are  re- 
quired. The  distillate  is  refined  with  sulfuric  acid  and  fractioned 
into  different  grades  of  lubricating  oil.68  These  deposits  have  been 
worked  for  many  years,  and  over  100,000  tons  are  mined  annually 
for  use  on  the  continent  of  Europe.  The  material  as  mined  requires 
no  further  treatment,  other  than  grinding.  It  is  shipped  from  the 


IX  EUROPE  211 

ports  of  Siracuse,  Mazzarelli  and  Catania.    Analyses  show  the  fol- 
lowing compositions : 

Range  Average 

Per  Cent  Per  Cent 

Asphalt 8.80-14.05      9.24 

Calcium  carbonate 82.15-88.21  87.98 

Iron  and  aluminium  oxides 0.91—  1.90  0.93 

Magnesium  carbonate 0.96  0.72 

Silica o .  60-  o .  73  o .  69 

Moisture  and  loss 0.40-  i .  17  0.76 

The  extracted  asphalt  shows  the  following  penetrations  (Test 
9&)  :  At  77°  F.  too  soft;  at  60°  F.  168;  at  50°  F.  94;  at  40°  F.  50. 
The  fusing-point  (Test  i$b)  ranges  between  36  and  44°  C. 


FIG.  70. — Sawing  Ragusa  Asphalt  into  Blocks. 

The  rock  asphalt  is  also  removed  in  large  blocks  which  are 
capable  of  being  sawed,  bored,  or  carved  in  the  form  of  paving 
stones,  stair  treads,  or  ornamental  work  for  buildings.  The  dark 
color  of  the  asphalt  as  freshly  mined  soon  disappears  upon  expo- 
sure to  the  weather,  turning  to  a  bluish  gray. 

Smaller  deposits  occur  at  Modica  and  Scicli,  south  of  Ragusa, 
in  the  same  region,  testing  as  follows:  moisture  0.60  to  0.72  per 


212  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

cent,  asphalt  9.00  to  9.50  per  cent,  CaCO8  87.27  to  86.78  per  cent, 
Fe2O3  2,05  per  cent,  SiO2  0.78  to  0.72  per  cent,  and  loss  0.30  to 
0.23  per  cent.  Asphalt  is  abundant  in  the  basalt  at  Cozzo  Grillo, 
near  Cape  Passero,  at  the  southeastern  tip  of  Sicily,  also  at  Vizzini, 

north  of  Ragusa. 

GREECE  6* 

Department  of  Triphylia.  At  the  village  of  Marathonpolis,  on 
the  west  coast  of  the  Pteloponnesus  District,  there  occurs  a  deposit 
of  asphaltic  limestone  well  suited  for  the  preparation  of  asphaltic 
mastic  pavements,  analyzing  as  follows:  asphalt  14.75  per  cent,  si- 
lica 1.07  per  cent,  iron  and  aluminium  oxides  0.80  per  cent,  calcium 
sulfate  0.21  per  cent,  magnesium  carbonate  0.45  per  cent,  calcium 
carbonate  82.27  per  cent,  moisture  and  loss  0.45  per  cent  This  de- 
posit is  shown  in  Fig.  71,  location  2. 

Department  of  Achaia  (Peloponnesus  District).  Asphalt  has 
also  been  reported  at  location  3,  likewise  at  location  4  (Fig.  71) 
near  Divri,  south  of  Mount  Olonos,  and  north  of  the  town  Souli. 

lolian  Islands.  Liquid  asphalt  deposits  occur  on  the  island  of 
Zante  (Zacynthus  or  Zakynthos)  at  location  5  (Fig.  71  ),70  and 
asphaltic  limestone  on  the  islands  of  Paxos  and  Antipaxos,  as  shown 
at  location  6. 

Department  of  Phocis.  A  deposit  has  been  reported  near 
Galaxidi,  shown  at  location  7  (Fig.  71). 

Department  of  Phthiotis.  Occurrences  are  found  near  Dremisa 
(Dramesi)  as  indicated  at  location  8  (Fig.  71). 

Departments  of  Eurytania  and  Arta.  Occurrences  of  soft 
asphalt  and  asphaltic  limestone  are  found  in  the  Pindus  Mountains, 
up  to  the  town  of  Pinde,  as  shown  in  locations  9,  10,  n  and  12 
(Fig.  71).  Location  n  is  at  Vordo,  in  the  valley  of  the  Molitsa 
River,  a  branch  of  the  Kalamas  River. 

Northern  Departments.  Various  outcrops  of  asphalt  have  been 
found  at  Bajousous  (location  13),  Lavdani  (location  14)  and 
Eleousa  (location  14),  in  the  Northern  Provinces,  Fig  71. 

,  PORTUGAL 

Province  of  Estremadura.  At  Serra  de  Cabagoa  deposits  of 
asphaltic  sandstone  have  been  reported,  and  at  Monte  Real,  north 
of  <Leiria,  layers  of  asphaltic  sandstone  impregnated  with  a  very 


DC 


EUROPE 


213 


soft  and  viscous  asphalt  exist  None  of  these  have  been  worked  to 
any  great  extent  An  asphalt  pit,  known  as  "Azeche,"  was  formerly 
worked  south  of  Nuestra  Senora  de  la  Victoria.71 


0       25     50      75     100 

I      ii       db 
KILOMETRES 


FIG,  71.— Map  of  Greek  Asphalt  Deposits. 
SPAIN  r2 

Province  of  Santander.  In  the  neighborhood  of  Puerto  del 
Sscudo,  deposits  of  asphaltic  sandstone  are  found  in  beds  about  5  ft. 
:hick.  No  analyses  are  available.  At  Suances  similar  deposits  of 


214  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

asphaltic  sandstone  have  been  reported  containing  approximately 
1 1  per  cent  of  asphalt,  also  in  the  Reviere  of  Lucara. 

Province  of  Alava.  At  Alauri,  Maestu,  and  other  localities  in 
the  Pyrenees,  asphaltic  sandstone  deposits  containing  12  to  20  per 
cent  of  asphalt  have  been  worked  for  a  number  of  years.  A  mine 
about  10  miles  from  Vittoria  consists  of  a  calcareous  sandstone  in> 
pregnated  with  8  to  9  per  cent  of  asphalt.  It  shows  the  following 
average  composition: 

Asphalt „ 8 . 80  per  cent 

Silica 68.75  per  cent 

Iron  and  aluminium  oxides 4.35  per  cent 

Calcium  carbonate 9. 15  per  cent 

Magnesium  carbonate 8.10  per  cent 

Water  and  loss 0.85  per  cent 

Province  of  Navarre.  Similar  deposits  have  been  reported  at 
Bocaicoa,  which  have  been  worked  to  a  limited  extent. 

Province  of  Gerona.  Asphalt  and  asphaltic  shales  have  been 
found  in  the  neighborhood  of  Can  Dabano,  associated  with  ozo- 
kerite. The  asphalt  melts  at  61.5°  C.  (K.  and  S.  method). 

Province  of  Tarragona.  Asphalt  occurs  in  the  District  of 
Campius,  in  the  precipices  of  Montseng,  also  at  Sot  del  Bosch,  Port 
B6,  Can  Call,  Sot  de  Puig  and  El  Sotas.  Likewise  in  the  District 
Manresa  in  the  Santa  Catalina  Mountains.  Asphaltic  shales  occur 
in  the  District  Saedes  *at  Ribas  de  la  Pega,  Serrat  Negre,  Clara 
and  Canal  de  Dordella. 

Province  of  Soria,  At  Santander,  Sierra  de  Frentes,  and 
Fuente-toba-Cidones,73  several  deposits  of  asphaltic  sandstone  have 
been  operated,  from  which  fairly  large  quantities  have  been  mined. 

Province  of  Burgos.  In  the  Reviere  of  Huidobro,  Asphalt  pits 
have  been  worked  at  Narcisa  and  Felicia. 

Province  of  Almeria.  Asphalt  has  been  reported  at  Cobdar, 
Tijola  and  Bayarque. 

Province  of  Valencia.    Asphalt  has  been  reported  at  Mogente. 


74 


RUSSIA  (IN  EUROPE) 

Simbirsk  Province.  The  principal  occurrences  are  found  along 
the  banks  of  the  Volga  River  in  the  vicinity  of  the  estuaries  of  vari- 
ous small  streams,  including  the  Syzranka,  extending  to  Samarskaya- 


IX  EUROPE  215 

Louka,  between  the  village  Perewoloki  and  the  city  Syzran.  These 
contain  6-13  per  cent  asphalt  (rarely  37  per  cent)  associated  with 
dolomite.  In  the  same  region,  north  of  Samarskaya-Louka  and 
3  km.  from  the  Volga  River,  there  occurs  a  deposit  containing  6-20 
per  cent  asphalt  associated  with  sand,  known  as  "garj,"  covering  an 
area  1300  by  320  ft.,  in  a  layer  32  ft.  deep.  The  extracted  asphalt 
has  a  fusing-point  of  96-147°  C.T5 

Kazan  Province.  Deposits  have  been  reported  at  Chistopol  on 
the  Kama  River. 

Samara  Province.  Asphalt  is  found  at  the  mineral  wells  at 
Sergievsk,  also  at  Sarabik-Ulowo  and  Chugorowo  in  the  vicinity  of 
Bugulma.  Deposits  are  found  near  Samara,  at  the  hair-pin  bend  of 
the  Volga,  also  at  Tzarevstchina  and  on  the  banks  of  the  Krunza 
and  Oussa  Rivers,  between  Kostyachi  and  Petcherskoi'e. 

Terek  Province  (Northern  Caucasia).  At  Vladikavkaz  there 
occurs  a  deposit  containing  6—12  per  cent  soft  asphalt  associated 
with  earthy  matter.  This  is  known  as  "kir"  when  found  in  a  fairly 
pure  state,  and  "katran"  when  associated  with  much  mineral  mat- 
ter. Also  4  km.  north  of  Staniza-Miailovskaja  there  occurs  a  de- 
posit in  a  ravine  of  the  mountain  Besimyannya-Gora,  containing  70 
to  86 y^  per  cent  asphalt  associated  with  clay.  The  extracted  as- 
phalt is  hard  and  brittle,  melting  at  about  300°  C,  and  has  a  specific 
gravity  of  about  i.2.76  Deposits  also  occur  at  Goriatchevodsk,  like- 
wise on  the  banks  of  the  Little  Chetchna  River,  between  the  Terek 
and  Argun  Rivers.  Asphaltic  sands,  sandstone  and  clay  occur  near 
the  town  Sernowodsk.  North  of  the  Groznyi  oil  fields  there  occurs 
a  deposit  containing  6  to  1 2  per  cent  asphalt,  likewise  several  small 
deposits  on  the  Groznyi  and  Terek  rocky  prominences  in  the  vi- 
cinity of  the  oil  wells. 

Kutais  Province  (Transcaucasia).  In  the  vicinity  of  Sukhum,  on 
the  left  bank  of  Bzyb  River,  there  occur  veins  of  asphalt  in  dolomite, 
in  the  Bsyschro  basin.  Near  Ozurgeti,  about  3  km.  north  of  the 
railroad  station  Notanebi  there  occur  deposits  of  asphaltic  sandstone 
containing  20  per  cent  asphalt.  A  large  deposit  occurs  i  km,  from 
the  left  bank  of  Supsa  River,  near  where  it  empties  into  the  Black 
Sea,  to  the  west  of  Chrialeti  mountain.  Deposits  are  reported  near 
the  village  Guriamta  and  asphaltic  sands  in  the  vicinity  of  Tamara- 
sauli,  likewise  in  the  valley  of  Bekwis-Zchali  River,  near  the  town 


216  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

Bekwi,  also  at  the  village  Dsmuisi  about  25  km.  northeast  of  the 
city  Kutais* 

Tiflis  Province  (Transcaucasia).  Asphalt  deposits  occur  in  the 
neighborhood  of  Gori,  also  the  village  Dschawa  at  the  overflow  of 
the  Big  Ljachwa  River.  Near  Signach,  about  2  km.  northeast  of 
the  Mirsaani  oil  field,  in  the  Kwamianzkaro  ravine,  there  occur  four 
veins  of  hard  asphalt  containing  26.3-30.6  per  cent  ash.  Asphaltic 
sandstones  are  found  on  the  right  bank  of  the  Yora  River  near 
Chatma,  Kapitschi,  and  in  the  rocky  prominences  of  Eilar-Augi  near 
the  town  Kasaman. 

Baku  Province  (Transcaucasia).  Near  Baku  there  are  a  num- 
ber of  deposits  of  asphalt  in  the  vicinity  of  the  oil  wells,  and  in  the 
region  of  the  numerous  large  mud  volcanos.  In  the  Adzhikabul 
(Adza  Kabul)  district,  about  75  km.  southeast  of  Baku,  a  deposit 
of  rock  asphalt  has  been  reported  containing  42-67  per  cent  soluble 
in  carbon  disulfide.  The  extracted  asphalt  has  the  characteristics 
of  gilsonite,  testing  as  follows : 77 

(Test    7)  Specific  gravity  at  77°  F 1.026-1.081 

(Test    9^)  Penetration  at  77°  F o  to  9 

(Test  15^)  Fusing-point  (R.  &  B.  method) 196-268°  F. 

(Test  19)  Fixed  carbon 13.6-15.9  per  cent 

On  the  Island  Suyatoi  there  is  an  area  of  about  14  hektar  cov- 
ered with  asphalt,  which  however  is  not  utilized. 

ASIA 

SYRIA  (LEVANT  STATES)  78 

The  deposits  which  follow  are  indicated  on  the  map  shown  in 
Fig.  72. 

Vilayet  of  Aleppo.  Various  deposits  of  asphaltic  limestone  have 
been  reported  about  5  miles  south  of  Alexandretta,  also  near  An- 
takia  (Antioch). 

f  Vilayet  of  Beirut  At  Jebel  Keferie  (Jebel  Kfarieh),  a  hill  near 
the  bend  of  the  Nahr  el  Kabir,  near  the  town  Babenna,  about  38 
km.  from  the  sea,  on  the  road  between  Latakia  and  Aleppo,  exten- 
sive deposits  of  asphalt  are*  found  covering  an  area  of  1400  by 
1500  m.,  estimated  to  contain  about  2,000,000  tons.  Most  of  these 
consist  of  a  dolomitic  marl  (containing  28.0  per  cent  silica,  2.9  per 
cent  MgCO8  and  3.0  per  cent  clay)  with  asphalt,  of  which  21.0  to 


IX 


ASIA 


217 


FIG.  72.— Map  of  Asphalt  Locations  in  Syria  and  Palestine. 


218  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

23.6  is  soluble  in  carbon  tetrachloride  and  10.9  to  10.3  per  cent  of 
the  non-mineral  matter  remains  insoluble.  The  bituminous  con- 
stituents are  associated  with  68.1  to  66.1  per  cent  mineral  con- 
stituents (total  =  100  per  cent).  These  deposits  have  not  been 
worked  to  any  extent,  on  account  of  the  difficulty  in  transportation 
to  the  coast.79  They  occur  in  three  separate  valleys  or  canons,  i.e., 
Chandak  bu  Sfgherie,  Chandak  Shehade,  and  Chandak  el  Barbura; 
likewise  on  the  neighboring  mountains,  Jebel  Harf  and  Jebel  Nobeh. 
Similar  deposits,  but  of  a  smaller  size,  pccur  west  of  the  foregoing, 
and  north  of  a  small  canon  through  which  the  Nahr  el  Kebir  passes, 
at  Dahana  (Derhana,  or  Derk'ah'a),  consisting  of  limestone  and 
serpentine  impregnated  with  asphalt,  of  which  10.7  to  12.3  per  cent 
is  soluble  in  CC14;  also  at  Milik,  consisting  of  asphaltic  marl,  of 
which  6.93  per  cent  is  soluble  in  CC14  and  4.34  per  cent  non-mineral 
matter  remains  insoluble;  likewise  at  Jebel  Sullas  (Sulas),  consist- 
ing of  limestone  and  marl  impregnated  with  asphalt,  of  which  6.99 
per  cent  is  soluble  in  CC14  A  still  smaller  deposit  lies  north  of  the 
last  three,  at  Djukr  Djak,  near  Kabara.  Still  another  deposit  oc- 
curs close  to  the  city  of  Beirut,  and  a  small  one  near  Tyre  (Es  Sur). 
Other  deposits  are  reported  at  Ain  Ibl  (Ain  Ebel)  20  miles  south- 
east of  Tyre;  at  Aidib  (Aideb)  15  miles  east  of  Tyre;  and  at 
Hereika.80 

Vilayet  of  Sham  (Syria).81  Asphaltic  limestone  deposits  are 
reported  at  Khaliwet,  between  Hasbaya  (Hasbeya)  and  Rashaya 
(Rasheye),  also  at  localities  5  miles  southeast  of  Hasbaya;  another 
10  miles  south  of  Hasbaya;  another  at  Sohmor  (Sahmur)  10  miles 
north  of  Hasbaya  on  the  eastern  bank  of  the  Nahr  Litani ;  another 
at  Ain-et-Tineh  7  miles  north  of  Hasbaya  on  the  western  bank  of 
the  Nahr  Litani;  and  still  another  4  miles  north  of  Hasbaya  at  Ain 
Tannura  (Ain  Tadjoura).  Asphaltic  limestone  deposits  occur  in 
the  Yarmuk  (Jarmuk)  River  valley,  along  the  Damascus-Haifa 
railroad,  at  Marani  (Mrani)  containing  10  to  30  per  cent  asphalt; 
also  at  El-Makarin  (Mekarim)  containing  18  to  20  per  cent  asphalt. 
Rock  asphalt  also  occurs  northeast  of  Latakia,  north  of  Horns,  and 
about  25  miles  west  of  Tyre. 

Palestine.  Deposits  of  asphaltic  limestone  occur  at  the  Sea  of 
Galilee  (Lake  Gennesaret,  or  Bahr  Tubariya),  at  Tubariya  (Ti- 
berias) and  Hammath  (Amman,  Hamath,  or  Hammam)  on  the 


IX  ASIA  219 

western  shore,  also  at  Muskes  on  the  River  Jordan  south  of  the  Sea 
of  Galilee*  Asphaltic  limestone  deposits  also  occur  at  the  Dead  Sea, 
the  largest  being  at  Nebi  Musa  (Neby  Musa)  4  miles  west  of  the 
northwest  shore.  This  is  reported  to  carry  4  to  6  per  cent  of  as- 
phalt and  has  a  black  color.  A  typical  analysis  is  as  follows :  asphalt 
soluble  in  chloroform  5.07  per  cent,  CaCO3  70.20  per  cent,  MgCO3 
trace,  CaSO4  1.20  per  cent,  SiO2  4.51  per  cent,  A12O3  and  Fe2O3 
6,56  per  cent,  insoluble  organic  mattter  12.52  per  cent,  total  100,06 
per  cent.  Other  deposits  are  found  on  the  western  shore  near  Es 
Sebba  (Es  Sebbe,  or  Es  Sebeh)  and  Wadi  Sebba  (Wadi  Sebeh,  or 
Wadi  Sebbeth).  A  short  distance  from  these  localities,  there  occurs 
a  peculiar  deposit  consisting  of  flint  pebbles  cemented  together  with 
varying  percentages  of  asphalt,  in  juxtaposition  to  a  vein  of  asphal- 
tic  limestone.  Deposits  of  asphaltic  limestone  are  also  reported  on 
the  eastern  shore  near  El  Kerak.  On  the  southwestern  shore,  at 
the  foot  of  Jebel  Usdom  ( Jebel  Esdom)  mountain,  is  found  a  con- 
glomerate carrying  asphalt  as  the  binding  medium,  and  close  to  this 
locality,  about  300  yards  from  the  mouth  of  the  Wadi  Mahawat 
(Wadi  Mayawat)  stream  there  occurs  a  deposit  of  asphaltic  lime- 
stone associated  with  fossil  marine  remains,  carrying  13  to  25  per 
cent  asphalt,  which  is  used  by  the  natives  as  fuel.82 

MESOPOTAMIA  (IRAQ) 

Villayet  of  Baghdad.  At  Hit,  to  the  west  of  Baghdad,  on  the 
west  bank  of  the  Euphrates  River,  deposits  of  asphaltic  limestone  are 
still  found  and  collected  by  the  natives  in  a  crude  way,  exactly  as 
was  the  case  many  centuries  ago.  The  occurrences  are  found  a  short 
distance  south  of  Hit,  between  two  streams,  the  Kubessah  and  the 
Mohammedieh.  The  asphalt  is  collected  and  sold  in  the  form  of 
small  cakes,  which  the  Turks  call  "karasakiz"  and  the  Arabs  "jir" 
or  "ghir"  or  "gir" — referring  to  a  mastic  containing  sand  or  lime- 
stone. The  term  "seyali"  is  used  to  designate  the  fluid  or  semi- 
fluid varieties  of  asphalt  of  recent  origin,  and  the  term  uqasat"  to 
denote  the  ancient  forms  of  natural  asphalt.  Upon  being  melted 
and  mixed  with  sand  or  earth,  it  is  used  for  calking  ships.  Asphalt 
deposits  4  to  5  m.  thick  are  found  at  Tuz-Khurmatli  on  the  west 
bank  of  the  Tigris  River,  about  50  miles  north  of  Baghdad.  South- 
west  of  this  locality  there  occurs  a  deposit  about  2  m.  thick,  at  the 


220  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

springs  of  Kifri,  about  2  miles  east  of  the  settlement  at  the  foot  of 
Neft-Dagh  (Naphtha  Mountain).88  Another  deposit  occurs  on 
Karum  River,  north  of  Dizful,  a  short  distance  north  of  the  Persian 
Gulf.  Another  deposit  has  been  reported  on  the  southeastern  slope 
of  Jebel  El-Hamrin  mountain  along  the  Tigris  River. 

ASIATIC  RUSSIA 

Uralsk  Province.  A  deposit  of  asphaltic  sand  occurs  on  the  road 
from  Chiwa  and  Kungrad  towards  Uil  and  Uralsky,  about  25  km. 
northeast  of  the  village  Tersekan,  on  the  southern  shore  of  a  small 
salt  lake. 

State  of  Turkestan.  Asphalt  deposits  occur  on  the  island  of 
Cheleken  at  so-called  Naphtha  Mountain  (Neftjanaja  Gora)  and 
in  several  other  localities,  particularly  in  the  vicinity  of  Ferghana, 
from  which  region  about  1500  tons  of  rock  asphalt  are  exported  to 
Europe  annually. 

Kamchatka  Peninsula  (Eastern  Siberia).  On  the  tundra  of  the 
western  coast  of  Kamchatka,  north  of  the  River  Sopotschnyi,  as- 
phalt deposits  have  been  reported. 

Sakhalin  Island.  More  or  less  developed  deposits  of  rock 
asphalt  occur  on  the  northern  portion  of  the  island. 

TlJRKEY-IN-AsiA    (ASIA    MlNOR) 

Anatolia.  Several  minor  deposits  of  rock  asphalt  have  been 
reported  to  occur  in  Anatolia,84  and  at  Olty  (Olti)  in  the  State  of 
Georgia,  but  these  are  of  no  particular  commercial  importance. 

ARABIA 

Vilayet  of  El  Hasa.85  In  1902  an  extensive  deposit  was  dis- 
covered on  the  island  of  Bahrein,  in  the  Persian  Gulf,  which  on 
analysis  was  found  to  consist  of: 

Asphalt. . . , aa. 77  per  cent 

Ash 76 . 68  per  cent 

Moisture ,,      o,  59  per  cent 

Total , 100,04  P«r  cent 

The  ash  consists  almost  exclusively  of  calcium-aluminium  silicate. 
The  product  is  mixed  with  limestone  powder  and  used  for  paving 


IX  ASIA  221 

purposes.  Another  deposit  is  found  near  Burgan  on  the  west  shore 
of  the  Persian  Gulf  and  west  of  Ai-Koweit  (Koweyt)  near  the  town 
of  Benaid-el-Qar. 

Sinai  Peninsula.  Asphaltic  petroleum  seepages  occur  at  Abu 
Durban  and  Jebel  Tanka. 

EGYPT 

Springs  of  asphalt  oil  have  been  known  as  far  back  as  Roman 
times  to  exist  at  Jebel  Zeit,  termed  by  them  "Mons  Petrolius,"  be- 
tween the  Nile  and  the  Gulf  of  Suez.  Layers  of  asphaltic  sand- 
stone have  recently  been  reported  at  Helwan,  on  the  right  bank  of 
the  River  Nile,  a  short  distance  south  of  Cairo.86 

INDIA 

Kashmir  District.  Rock  asphalt  has  been  reported  near  Isakhel 
ontheBasti  River. 

Hazara  District,  Seepages  of  impure  liquid  asphalt  occur  in 
the  Sierra  Mountains  at  Gunda. 

Baluchistan  District.  Asphalt  seepages  similarly  occur  at  Gan- 
dava  and  Khalan  (Khar an), 

Bombay  Island.  Deposits  of  umineral  pitch"  and  basalt  have 
been  reported  in  Bombay  Island,  off  the  western  coast  of  India.87 

CHINA 

Chinese  Turkestan  (Sin-Kiang),  In  Sungaria  (Dzungaria), 
asphalt  deposits  have  been  reported  at  Lake  Telli-Nor  in  the  Dzung 
Gobi,  southeast  of  Jair  Mountains;  also  at  the  Orchu  Basin  of  the 
Jeun  River,  on  the  southern  slope  of  Jair  Mountain. 

JAPAN 

Akita  Prefecture.88  A  series  of  asphalt  deposits  occur  in  the 
villages  of  Toyokawa  (embracing  the  hamlets  of  Tsukinoki,  Riuge, 
Magata,  Iwase  and  Urayama)  and  Kanaashi  (embracing  the  hamlet 
of  Kurokawa}.  These  are  situated  between  i  to  \y2  miles  east  of 
the  Okybo  railway  station  on  the  Ou  railroad  line,  in  the  neighbor- 
hood of  Lake  Hachiro  and  the  pond  Iwase.  From  the  area  cov- 
ered by  the  deposits,  about  180,000  sq.  ft.,  it  is  estimated  there  exist 
a  total  of  2,360,000  cu.  ft  in  volume.  They  are  found  on  the  sur- 


222 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


face  of  the  hills  about  30  to  50  meters  above  sea  level,  also  among 
the  swamps  surrounding  the  hills.  It  is  apparent  that  this  region 
is  underlaid  with  an  asphaltic  petroleum  which  seeps  out  between 
the  fissures  in  the  shales  and  flows  out  of  springs  in  the  bottom 
of  the  swamps  or  marshes.  For  example,  in  the  pond  Iwase,  the 
natives  stir  the  bottom  with  a  long  bamboo  pole,  which  detaches 
masses  of  soft  asphalt,  which  are  then  ladled  from  the  water's 
surface.  The  asphalt  occurs  in  various  forms,  depending  upon  the 


FIG.  73. — Mining  Asphalt  at  Toyokawa,  Japan. 


state  of  weathering  and  the  associated  ingredients,  ranging  from 
a  thick  viscous  maltha  to  a  hard  solid  form  associated  with  sand 
or  clay,  and  in  swamps  with  the  decayed  remains  of  aquatic  plants. 
As  the  asphalt  exists  near  the  surface  of  the  earth,  it  is  mined  by 
hand  with  a  spade  or  mattock,  as  illustrated  in  Fig.  73.  After  ex- 
posing it  to  the  sun  for  a  while,  it  is  melted  in  shallow  pans  to  expel 
the  water  and  permit  the  coarse  earthy  matters  and  organic  im- 
purities to  settle,  whereupon  the  asphalt  is  cast  into  moulds  and 
marketed  as  such.  This  operation  has  been  performed  in  much 
the  same  way  since  ancient  times.  The  good,  rich  ore  is  lustrous 


IX 


AUSTRALIA 


and  black,  whereas  the  lean,  poor  ore  appears  dull  brown, 
made  by  the  author  gave  the  following  results: 


223 
Tests 


Crude 

Fluxed 

Asphalt 

Asphalt 

(Test    i)     Color  in  mass  

Black 

Black 

(Test    2)     Homogeneity  

Non-homogeneous 

Homogeneous 

(Test    4)     Fracture  

Conchoid  al 

Conchoidal 

(Test    5)     Lustre  

Dull 

Bright 

(Test    6)     Streak  

Brown 

Black 

(Test    7)     Specific  gravity  at  77°  F  

1.280 

1.075 

(Test    9^)   Penetration  at  1  1  5°  F  

13 

65 

Penetration  at  77°  F  

0-3 

!5-5 

Penetration  at  32°  F  

0 

2.3 

(Test    9^)    Consistency  at  1  1  5°  F  

30-7 

10.6 

Consistency  at  77°  F  

83-4 

27.6 

Consistency  at  32°  F  

Over  too 

66.9 

(Test    9^)   Susceptibility  index  

Over  33 

31.8 

(Test  io£)    Ductility  at  77°  F  

o 

i 

(Test  i  $£)   Fusing-point  (R.  and  B.  ) 

210°  F. 

i54i°F. 

(Test  1  6)     Volatile  at  325°  F.,  5  hrs  

2  .  2    per  cent 

2.8    percent 

(Test  19)     Fixed  carbon  

20.7    percent 

20.9    percent 

(Test  21)     Soluble  in  carbon  disulfide.  .  .  . 

47.72  per  cent 

86.88  percent 

Non-mineral  matter  insoluble.  . 

36.85  percent 

9.25  per  cent 

Mineral  matter  

15.43  P^  cent 

3.87  per  cent 

Total  

loo.oo  per  cent 

loo.oo  per  cent 

(Test  22)     Carbenes  

0.42  per  cent 

0.12  per  cent 

(Test  23)     Asphalt  soluble  in  petroleum 

naphtha  

23  .  2    per  cent 

60.3    percent 

(Test  33)     Solid  paraffins  

0.2    percent 

0.5    percent 

(Test  340)  Asphalt  as  saturated  hydrocar- 

bons   

10.5    percent 

26.8    percent 

The  production  ranges  from  2000  to  4000  tons  annually. 

Prefectures  of  Yamagata,  Aomori  and  District  of  Hokkaido. 
Minor  deposits  have  been  reported  at  these  localities,  but  have 
attained  no  commercial  importance. 


AUSTRALIA 

New  South  Wales.  Several  occurrences  have  been  reported  in 
New  South  Wales.89 

Western  Australia.  Minor  deposits  have  been  found  in  the 
Ord  River  basin,  150  miles  south  of  Wyndham,  near  the  junction 
of  the  Ord  and  Negri  Rivers;  likewise  along  the  Stirling  River.90 

Northern  Territory.  An  occurrence  has  been  reported  at  the 
Waggon  Lagoon,  on  Roper  River,  350  miles  east  of  Port  Darwin.90 


224 


ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER 


IX 


Tasmania.  Asphalt  deposits  have  been  reported  between  Re- 
cherche Bay  and  New  River  in  southern  Tasmania.81 

New  Zealand.  Asphalt  deposits  have  been  located  in  the  Man- 
gawai  and  Arai  Districts,  between  Bream  Tail  and  Rodney  Point. 


DUTCH  EAST  INDIES 

Buton  (Boeton)  Island.  An  extensive  asphalt  deposit  occurs 
on  Buton  Island,  south  of  Celebes  Island.92  Illustrated  in  Figs.  74 
and  75,  Four  different  mines  have  been  reported. 

(1)  Kaboengka,  estimated  to  contain  approximately  1,200,000 
tons  of  asphaltic  limestone, 

(2)  Lawele,  estimated  to  contain  100  million  tons  of  asphaltic 
marl. 

(3)  Waisioe. 

(4)  Wariti. 

The  composition  of  the  asphalt  is  as  follows : 


Kaboengka 

Lawele 

Waisioe 

(A) 

(B) 

(A) 

(B) 

Crude  Asphalt: 
Water  

i-S% 
37-39% 

0,2-!% 

58-6i% 

1.09-1.12 
6-1  8 
61-69 

1  2-1  IO 
23.7-29.0% 

2% 
26-27% 

°.5~2% 
70-72% 

i.  06 
65 

5i     ' 
no 

24-5% 

2% 

25-35% 
0.5-2% 

65-75% 

10-20% 
50-60% 
2-10% 
10-40% 

1-5% 
35~37% 

0.2-1% 
61-63% 

I.Op 
10 

64 

32 
25.9% 

Asphalt  

Organic  matter.  .  .  ,  .  ,  ,  

Mineral  matter.  .  ,  >  

Extracted  Asphalt: 
SD.  ffr.  at  77°  F  

1.  06 

73 
47 
no 

25.7% 

Penetration  at  77°  F.  .  »  .   ... 

Fusing-point  (R.  and  B.)°  C. 
Ductility  at  77°  F  

Insol.  in  petr.  naphtha  (88°). 

The  mineral  matter  of  all  the  deposits  consists  of  microscopic 
shells  (globigerina  )  mixed  with  clay,  and  has  the  following  com- 
position: CaCOa  81.62-85.27  per  cent;  MgCO3  1.98-3.55  per  cent; 
CaSQ*  0.55-1.70  per  cent;  CaS  0.17-0.33  per  cent;  combined  water 
1*06-2.16  per  cent;  SiO2  6.95-9.15  per  cent;  Fe2Os  and  A1SO3  2.15- 
3<ii  p&r  cent;  undetermined  0.32*1*12  per  cent 


IX 


DUTCH  EAST  INDIES 


225 


0      10      20     30MU&S 


74, — Map  of  Buton  Asphalt  Deposits. 


FIG.  75. — Mining  Buton  Asphalt. 


226  ASPHALTS  ASSOCIATED  WITH  MINERAL  MATTER  IX 

AFRICA 

ALGERIA 

Province  of  Oran.  At  Constantine,  asphaltic  limestone  is  found 
in  veins  32  ft.  thick,  containing  as  much  as  40  per  cent  of  asphalt. 
In  many  places  the  rock  is  so  saturated  that  the  asphalt  seeps  out 
and  forms  pools  having  a  fusing-point  of  about  140°  F.  (K.  and  S. 
method),  a  penetration  of  1 1  at  77°  F.,  and  containing  0.9  per  cent 
of  sulfur.  The  limestone  is  largely  crystalline.  Deposits  have  also 
been  reported  at  Sidi  Messaoud.93 

NIGERIA 

Bituminous  sands  are  reported  in  southern  Nigeria  a  short  dis- 
tance from  the  coast  Attempts  have  been  made  to  purify  the 
asphalt  by  the  water-extraction  process,  but  so  far  this  has  resulted 
in  failure.  The  extracted  material  contains  about  70  per  cent  of 
asphalt,  10  per  cent  of  organic  substances  other  than  asphalt  and 
20  per  cent  of  sand. 

RHODESIA 

Rock  asphalt  has  recently  been  reported  in  northern  Rhodesia 
but  is  not  thoroughly  investigated.94 

MADAGASCAR 

Bituminous  sandstones  containing  3  to  6  per  cent  asphalt  have 
been  reported.95 


CHAPTER  X 


ASPHALTITES 

Asphaltites1  are  natural  asphalt-like  substances,  characterized  by 
their  high  fusing-points  (over  230°  F.).  They  are  grouped  into 
three  classes,  namely:  gilsonite,  glance  pitch,  and  grahamite.  Since 
all  are  presumably  derived  from  the  metamorphosis  of  petroleum, 
one  would  naturally  expect  the  classes  to  merge  into  one  another, 
and  such  actually  proves  to  be  the  case. 

The  author  has  adopted  the  following  means  of  differentiating 
the  three  classes,  one  from  another : 


Streak 

Specific 
Gravity 
at  77°  F, 

Softening-point 
(K.  and  S,  Method), 
Deg.  F. 

Fixed  Carbon, 
Per  Cent 

Gilsonite  or  Uintaite    .  .  . 
Glance  Pitch  or  Manjak* 
Grahamite  *  

Brown 

Black 
Black 

i  .05-1  .10 
i  .  10-1  .  1  5 
1.15-1.20 

230-350 
1130-350 
350-600 

10-20 
20-30 
3°-55 

*  When  substantially  free  from  mineral  matter. 

In  all  three  classes  the  non-mineral  constituents  are  almost  com- 
pletely soluble  in  carbon  disulfide.  The  physical  and  chemical 
characteristics  will  be  described  in  greater  detail  under  the  respective 
headings. 

GILSONITE  OR  UINTAITE 

This  asphaltite  is  found  in  but  one  region,2  extending  from  the 
eastern  portion  of  the  State  of  Utah  across  the  boundary  line  into 
the  western  portion  of  Colorado.  It  occurs  in  a  number  of  parallel 
vertical  veins,  varying  in  width  from  thin  fissures  to  several  feet. 

Gilsonite  was  first  discovered  by  the  early  settlers  in  about  1862, 
at  what  was  then  known  as  the  Culmer  vein,  several  miles  south  of 
the  present  town  of  Myton  in  Duchesne  County.  All  of  the  present 
veins  are  vertical  and  run  from  northwest  to  southeast.  The  gilson- 

227 


228  ASPHALT1TES  X 

ite  runs  fairly  uniform  in  composition,  and  complies  with  the  fol- 
lowing general  characteristics: 

(Test    i)     Color  mass Black 

(Test   4)     Fracture Conchoidal 

(Test    5)     Lustre Bright  to  fairly  bright 

(Test   6)     Streak Brown 

(Test   7)     Specific  gravity  at  77°  F 1.05-1.10 

(Test   90)  Hardness  on  Moh's  scale 2 

(Test  9^)  Hardness,  needle  penetrometer  at  115°  F,  3-8 
Hardness,  needle  penetrometer  at  77°  F.  0-3 
Hardness,  needle  penetrometer  at  32°  F.  o 

(Test   gc)  Hardness,  consistometer  at  115°  F 40-60 

Hardness,  consistometer  at  77°  F 90-120 

Hardness,  consistometer  at  32°  F Too  hard  for  test 

(Test    9^)   Susceptibility  index >  100 

(Test  lo*)  Ductility  at  77°  F.  (Author's  Method) . .  o 

(Test  t$a)  Fusing-point  (K.  and  S.  method) 230-350°  F. 

(Test  15^)   Fusing-point  (R  and  B  method) 270-400°  F. 

(Test  16)     Volatile  at  325°  F.,  5  hrs.  (dry  substance)  Less  than  2  per  cent 

Volatile  at  400°  F.,  5  hrs Less  than  4  per  cent 

Volatile  at  500°  F.,  5  hrs Less  than  5  per  cent 

(Test  19)     Fixed  carbon 10-20  per  cent 

(Test  21)     Soluble  in  carbon  disulfide Greater  than  98  per  cent 

Non- mineral  matter  insoluble o-i  per  cent 

Mineral  matter Trace-i  per  cent 

(Test  22)     Carbenes o-J  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 10-60  per  cent 

(Test  26)     Carbon 85-86  per  cent 

(Test  27)     Hydrogen 8. 5-10.0  per  cent 

(Test  28)     Sulfur 0.3-0.5  per  cent 

(Test  29)     Nitrogen 2.0-2.8  per  cent 

(Test  30)     Oxygen 0-2  per  cent 

(Test  33)     Solid  paraffins o-Trace 

(Test  34^)   Sulfonation-residue 85-95  per  cent 

(Test  37*)   Saponifiable  matter Trace 

(Test  39)     Diazo  reaction No. 

(Test  40)     Anthraquinone  reaction No. 

Gilsonite  is  assorted  and  marketed  in  two  varieties,  known  as 
"selects''  or  "firsts,"  and  "seconds"  respectively.  The  "firsts"  are 
taken  from  the  center  of  the  vein  and  are  characterized  by  a  con- 
choidal  and  lustrous  fracture.  The  "seconds"  occur  near  the  vein 
walls  and  are  characterized  by  a  semi-conchoidal  and  semi-lustrous 
fracture.  They  are  graded  at  the  mine  chiefly  by  their  appearance. 
The  firsts  have  a  higher  lustre,  a  lower  fusing-point,  a  greater  solu- 
bility in  petroleum  naphtha,  and  as  produced  at  the  mines  run  more 
uniform  in  physical  characteristics  than  do  the  seconds.  From  the 
middle  of  the  Cowboy  vein,  there  is  obtained  a  variety  of  gilsonite  of 
unusually  high  lustre,  having  a  deep  black  color  with  a  bluish  under- 


X 


GILSON1TE  OR  VINTAITE 


229 


tone,  known  to  the  trade  as  "jet  gilsonite,"  and  is  used  chiefly  in  the 
highest  grades  of  baking  enamels  and  japans.  It  melts  about  90°  F. 
higher  than  the  "selects."  The  "selects"  show  the  least  tendency 
to  gelatinize  when  dissolved  in  solvents,  the  "seconds"  a  moderate 
tendency,  and  the  "jet"  the  greatest  tendency.  The  three  grades 
test  as  follows: 

Selects 

Color  in  mass •   Black 

Fracture Conchoidal 

Lustre Bright 

Streak Brown 

Specific  grav.  at  77°  F.  i  .044 


Seconds 
Black 
Conchoidal 
Fairly  bright 
Brown 


'(Test  i) 
(Test  4) 
(Test  5) 
(Test  6) 

(Test   7)       .          _.  ,. 

(Test    go)  Hardness  (Moh's) 2 

(Test  i$a)  Fusing-point  (K.  and  S.)  230-240°  F.  240-280°  F. 
(Test  1 5^)  Fusing-point  (R.  and  B.)  270-300°  F.  275-325°  F. 
(Test  23)  Sol.  in  88°  petroleum 

naphtha 50-60%  20-50% 


1.049 

2 


Bluish  black 
Pencillated 
Very  bright 
Brown 
1.076 
a 

320-350°  F. 
350-400°  F. 


10-20% 


Figure  76  shows  the  hardness,  tensile  strength  (multiplied  by 
ro)  and  ductility  curves  of  a  mixture  of  gilsonite  and  residual  oil, 
fluxed  together  so  as  to  have  a  hardness  of  exactly  25.0  at  77°  F. 


100 
90 

eo 

70 
60 

?° 
40 

»A 

32*                          77°                     115° 

^ 

ttntrT~" 

91.0 

umumuiromim-m    / 

«•..»_.».«•  7 

lardness 
"ensf/e  Strength  x  10 
luctfltty 
Point*  142  °F. 
itib/Iiiy/ndex*4i7 

/ 

'"" 

'"X 

N, 

©  Fusing 
Suscef 

\ 

\ 

t 

% 

N 

S, 

> 

55.0 

v 

Sk 

^ 

V 

k 

\ 

* 

.. 

5 

in 

5V 

to 

10 

°i 

S 

2510s 

< 

\ 

/ 
/ 

\ 

S 

^ 

^s 

J! 

S 

—  IT- 
\ 

X 

'•2 

%^ 

^ 

*N 
6 

r 

>  '  • 
a^ 

N 
•-^^ 

V 

>     K>    20  -50   40    50    60    70    60   90    100   110   180    150  14?  150  tt 
Temperature,  Degrees  Fahrenheit 
FIG.  76.—  Chart  of  Physical  Characteristics  of  Fluxed  Gilsonite. 

(Test  9<;),  equivalent  to  a  penetration  of  20  at  77°  F.  (Test  gb). 
The  resulting  mixture  contained  gilsonite,  47  per  cent  and  resi- 
dual oil,  53  per  cent-  The  fusing-point  of  the  gilsonite  used  was 
285°  F.  (K.  and  S.  method),  and  that  of  the  resulting  mixture 
~ 


230  ASPHALTITES  X 

Gilsonite  is  one  of  the  most  valuable  asphalts  for  manufactur- 
ing paints  and  varnishes.  Gilsonite  and  glance  pitch  mix  readily 
in  ail  proportions  with  fatty-acid  pitches,  thus  differing  from  gra- 
hamite.  Products  involving  the  use  of  gilsonite  formed  the  basis 
of  several  patents  granted  to  S.  H.  Gilson,  after  whom  the  ma- 
terial  was  named.8 

Gilsonite  may  be  distilled  until  the  vapors  reach  a  temperature 
of  550°  F.,  when  an  exothermic  reaction  takes  place  and  the  evo- 
lution of  gaseous  products  becomes  exceedingly  rapid.  The  source 
of  heat  must  be  reduced  at  this  stage,  but  when  the  critical  point 
has  been  passed,  the  heating  may  be  continued  until  the  tempera- 
ture of  the  solid  coke  at  the  bottom  of  the  still  reaches  850°  F.4 
When  the  vapor  temperature  reaches  475  to  650°  F.  an  oily  dis- 
tillate is  obtained,  which  upon  refining  with  sulfuric  acid,  produces 
a  reddish  brown  oil  suitable  for  use  as  an  oil  substitute  in  making 
paints,5  and  the  sulfonation  product  may  be  used  to  hydrolyze  fats 
and  oils.6 

NORTH  AMERICA 

UNITED  STATES 
Utah. 

Uinta  County.  Practically  all  gilsonite  is  mined  in  the  "Uinta 
Basin/'  at  the  junction  of  the  Green  and  White  Rivers  south  of  Fort 
Duchesne,  Utah,  from  a  point  4  to  5  miles  within  the  Colorado 
boundary  line  (Rio  Blanco  County),  extending  westward  about  60 
miles  into  Utah.  A  large  number  of  veins  have  been  located  in  this 
area,  extending  from  a  northwesterly  to  a  southeasterly  direction, 
and  all  of  them  parallel  or  nearly  so.  The  veins  vary  in  width 
from  a  fraction  of  an  inch  to  1 8  ft.,  and  some  of  the  longest,  such 
as  the  Cowboy  or  Bonanza,  have  been  traced  8  miles.  The  veins 
are  almost  vertical  with  fairly  smooth  and  regular  rock  walls,  and 
although  they  are  usually  continuous,  they  may  in  certain  cases  be 
interrupted  in  the  direction  of  the  fissure.  Very  frequently  branch 
veins  join  the  main  one,  forming  very  acute  angles. 

Near  the  outcrop  where  it  has  been  exposed  to  the  weather, 
gilsonite  loses  its  brilliant  lustre,  changing  to  a  dull  black.  Along 
the  vein  walls  it  shows  a  columnar  structure,  extending  at  right 
angles  to  the  wall,  which  is  characteristic  of  all  asphaltites.  The 


X  GILSONITE  OR  VINTA1TE  231 

rock  walls  are  often  impregnated  with  gilsonite  */2  to  2  ft,  so  there 
is  no  visible  line  of  demarcation  between  the  impregnated  and  non- 
impregnated  portions.  In  shale  formation  the  impregnated  zone 
is  smaller  than  when  the  gilsonite  is  found  in  a  porous  sandstone. 
The  following  are  the  principal  veins  occurring  in  this  region: 

Duchesne  Vein.  This  occurs  about  3  miles  east  of  Fort  Du- 
chesne,  filling  a  vertical  crack  in  sandstone  and  shale.  The  vein 
has  been  traced  for  3  miles,  and  is  3  to  4  ft.  wide  for  about  I  y2 
miles,  tapering  at  the  ends,  until  it  completely  disappears,  A  com- 
paratively large  quantity  of  gilsonite  has  been  mined  from  this  vein. 

Culmer  Vein.  This  is  also  known  as  the  "Pariette  Mine," 
and  occurs  in  the  Castle  Peak  mining  district.  It  has  been  traced 
7  miles  and  varies  in  width  from  a  fraction  of  an  inch  to  30  in., 
averaging  about  a  foot.  Several  branch  veins  are  connected  with 
the  main  one  at  very  acute  angles.  It  also  shows  a  number  of 
transverse  faults  as  illustrated  in  Fig.  77,  in  which  the  lateral  dis- 
placements vary  from  I  to  10  ft.  The  associ- 
ated rock  consists  of  sandstone  and  shale. 

Bonanza  and  Cowboy  Veins.     These  em- 
brace three  veins,  known  as  the  Cowboy  vein, 
the  East  Branch  and  the  West  Branch  respec- 
tively of  the  Bonanza  Vein.     The  last  two  are 
joined  together  near  the  southern  end.    These 
veins  occur  in  sandstone  and  shale.    The  shale 
being  harder  than  the  sandstone,  seems  to  have 
offered  greater  resistance  to  the  intrusion  of 
gilsonite,  and  the  veins  are  not  therefore  as  wide 
when  they  occur  in  the  latter.    The  disappear- 
ance of  the  veins  to  the  northwest  also  occurs 
in  shales,  and  as  the  gilsonite  passes  from  sand-         * — fr  *    *   *** 
stone  into  shale,  it  splits  up  into  a  number  of  FIG.  77.— Faults  in  Gil- 
smaller  veinlets  which  gradually  thin  out  into  sonite  Vein, 
fine   hair-like    fissures.      The    Cowboy   is   the 
widest  vein  and  attains  a  maximum  width  of  18  ft.,  maintaining  for 
4  miles  a  width  of  8  to  12  ft,  as  shown  in  Fig.  78.    Its  total  length 
is  7  to  8  miles.    The  Bonanza  veins  have  similarly  been  followed 
for  7  miles,  but  they  are  not  as  wide  as  the  Cowboy. 

Dragon  group  of  veins  includes  the  original  Dragon  vein,  the 
Country  Boy  and  Rector  veins,  also  the  Rainbow  vein  abo*t  8  miles 
northeast.  These  occur  southwest  of  Evacuation  Creek,  a  tributary 
of  the  White  River,  near  the  Colorado  boundary  line.  They  extend 
about  4  miles  in  length  and  average  between  2  and  3  ft.  in  width. 


232 


ASPHALTITES 


X 


In  some  places  the  adjacent  rock  is  impregnated  with  the  gilsonite 
i  to  3  ft.  alongside  of  the  vein  proper.  In  191 1  an  explosion  shut 
down  the  Dragon  vein,  whereupon  the  operatives  have  been  trans- 
ferred to  the  Rainbow,  Country  Boy,  and  Rector  veins. 


Courtesy  of  American  Asphalt  Association. 
FIG.  78. — View  of  Cowboy  Gilsonite  Mine,  Utah. 

A  number  of  smaller  veins  occur  in  this  region,  including  the 
Uintah  vein,  with  its  branch  the  Little  Emma  vein,  also  the  Harri- 
son, Colorado,  and  other  veins. 


X 


GILSONITE  OR  UlNTAITE 


233 


A  branch  railroad,  known  as  the  Uintah  Railroad,  about  60 
miles  long,  runs  from  Dragon,  Utah,  connecting  with  the  Denver  & 
Rio  Grande  Railroad  at  Mack,  Col.,  and  then  extends  to  a  terminus 
at  Watson,  where  the  Rainbow  mine  is  located.  The  product  from 
the  Country  Boy  and  Rector  mines  must  be  trucked  3  to  5  miles, 


FIG.  79. — Gilsonite  Vein,  Rainbow  Mine,  Utah. 

and  that  of  the  Little  Emma  mine  is  trucked  to  Craig,  Colorado. 
These  four  mines  were  the  only  ones  which  are  operated,  producing 
in  aggregate  about  130  tons  daily.  Figures  79  and  80  show  two 
typical  views  of  the  Rainbow  mine. 

The  method  of  mining  is  very  crude,  and  consists  in  digging  into 
the  veins  until  a  slope  of  45  deg.  is  obtained.    The  gilsonite  is  then 


234  ASPHALTITES  X 

dug  from  the  face  of  the  slope,  rolled  down  to  the  bottom,  sacked 
and  hoisted  out.  The  hoisting  is  done  by  horses  at  shallow  levels, 
but  when  the  mine  becomes  over  200  ft.  deep,  machinery  must  be 
used.  Since  the  ore  is  brittle,  there  is  always  a  cloud  of  dust  in  the 
stopes  where  the  men  work,  which  is  soluble  in  the  lubricating  oil 


FIG.  80. — Interior  of  Rainbow  Mine,  Utah. 

used  with  compressed-air  mining  tools,  thus  interfering  with  the 
operation  of  such  tools.  Experience  has  therefore  shown  that  the 
production  per  man  is  greater  with  pick  and  shovel.  One  man  can 
mine  and  sack  an  average  of  2  tons  per  ten-hour  day.  Fires  are  a 
constant  danger,  as  the  dust  is  highly  inflammable,  and  explosions 
have  been  caused  by  a  chain  dropping  into  a  pit  and  striking  against 
the  rocky  walls,  causing  sparks. 


X  GILSONITE  OR  UINTA1TE  235 

Very  little  timber  is  required,  as  the  veins  are  nearly  vertical,  and 
the  surrounding  rock  is  firm  and  self-supporting.  Boulders  of  rock 
are  frequently  encountered  in  the  veins,  originally  detached  from 
the  sidewalls,  and  prove  a  serious  obstacle.  Blasting  can  only  be 
done  where  the  ventilation  is  perfect  and  there  is  no  gilsonite  dust, 
and  it  frequently  becomes  necessary  to  abandon  portions  of  the  vein 
on  this  account.  It  is  not  feasible  to  work  a  vein  less  than  2  ft. 
wide.  It  is  estimated  that  approximately  25  million  tons  of  gilsonite 
are  still  available  in  this  region. 

Oregon. 

Wheeler  County.  Minor  deposits  of  a  gilsonite-like  material 
have  been  reported  by  E.  T.  Hodge  T  in  the  vicinity  of  Clarno 
(Type  A)  ;  also  10  miles  east  of  Post  (on  the  Post-Paulina  high- 
way) ;  also  on  the  south  bank  of  Pine  Creek  near  Clarno  (Type  B), 
testing  as  follows: 

A"  Type"B" 


(Test    i)     Color  in  mass  ...............  Black  Black 

(Test   4)     Fracture  ...................  Conchoidal  Conchoidal  to  hackly 

(Test    5)     Lustre  .....................  Brilliant  Brilliant  to  dull 

(Test    6)     Streak  .....................  Brown  Brown 

(Test   7)     Specific  gravity  at  77°  F  ......  i  .07-1  .08  1  .07-1  .08 

(Test   90)  Hardness  ...................  2  .  aj 

(Test  1  5/*)  Fusing-point  (Note)  .........  525-550°  F*  625-650  F. 

(Test  16)     Volatile  325°  F.,  5  hrs  ........  o-i  per  cent  o-i  per  cent 

(Test  19)     Fixed  carbon  ................  5  .  i  per  cent  23  per  cent 

(Test  21)     Soluble  in  carbon  disulfide  .  .  .  98-99  per  cent  75  per  cent 

Non-mineral  matter  insoluble  1-1.5  per  cent  24.  5  per  cent 

Mineral  matter  ..............  0.5  per  cent          o  .  5  per  cent 

(Test  22)     Carbenes  ...................  i-i  .  5  per  cent  22  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naph- 

tha ......................  30  per  cent  p  per  cent 

NOTE.  The  fusing-points  are  somewhat  high  for  a  gilsonite,  and  approach  that  of  graham- 
ite.  The  above  materials  are  examples  of  border-line  cases.  Both  types  are  undoubtedly 
similar  materials,  and  Type  B  has  been  weathered,  so  that  its  original  characteristics  have 
been  altered.  Huntly  classes  "A"  as  a  gilsonite  and  "  B  "  as  a  grahamite. 

Crook  County.  A  prospect  has  been  located  38  miles  south- 
east of  Prineville,  on  Sec.  33,  T  16  S,  R  20  E.  (Willamette  meri- 
dian) ,  It  occurs  both  inside  and  outside  of  chalcedony-quartz-calcite 
geodes,  also  in  the  interstices  of  tuffaceous  sandstone,  likewise  in 
jasperoid  rock  alongside  a  dyke  of  rhyolite.  It  appears  that  the 


236  ASPHALTITES  X 

rhyolite  penetrated  and  fractured  an  oil-bearing  stratum,  allowing 
the  oil  to  ascend  along  the  wall  of  rhyolite.     It  tests  as  follows: 

(Test   i)    Color  in  mass Black 

(Test   4)     Fracture. . , Conchoidal 

(Test   5)    Lustre Very  bright 

(Test   6)     Streak Reddish  brown 

(Test   7)     Specific  gravity  at  77°  F 1.162 

Behavior  on  heating  in  flame Softens,  froths,  and  burns 

(Test  i$a)  Fusing-point  (K.  and  S.  method) 275°  F. 

(Test  21)     Soluble  in  carbon  disulfide 83.00  per  cent 

Non-mineral  matter  insoluble 16.39  per  cent  (Note) 

Mineral  matter o. 61  per  cent 

Total 100.00  per  cent 

NOTE.    Consists  of  brown  powder,  which  swells  up  in  carbon  disulfide,  or  when  heated. 

This  asphaltite  appears  to  be  a  metamorphized  gilsonite.  Only 
part  is  soluble  in  residual  oil  (asphaltic),  also  linseed  oil,  but  on 
prolonged  heating  the  insoluble  matter  depolymerizes  and  gradually 
goes  into  solution. 

ASIA 

RUSSIA 

Archangel  Province.  A  hard  asphaltite,  closely  resembling  gil- 
sonite, having  a  specific  gravity  at  77°  F.  of  1.0887  and  a  fusing- 
point  (K.  and  S.  method)  of  240°  F.  has  been  reported8  in  the 
Ukhta  district  on  the  Izhma  River. 


GLANCE  PITCH 

Glance  pitch  resembles  gilsonite  in  its  external  appearance,  with 
the  exception  of  the  streak,  which  is  a  decided  brown  in  the  case  of 
gilsonite,  and  black  in  the  case  of  glance  pitch.  It  also  differs  in 
having  a  higher  specific  gravity  and  producing  a  larger  percentage  of 
fixed  carbon.  It  always  has  a  brilliant  conchoidal  fracture,  and  a 
fusing-point  between  230  and  350°  F.  (K,  and  S.  method).  In 
general,  glance  pitch  complies  with  the  following  characteristics: 

(test  i)  Color  in  mass Black 

(Test  4)  Fratture, , *  Conchoidal  to  hackly 

(Test  5)  Lustre Bright  to  fairly  bright 

(Test  6)  Streak  on  porcelain Black 

(Test  7)  Specific  gravity  at  77°  F 1.10-1.15 


X  GLANCE  PITCH  237 

(Test   90)  Hardness,  Moh's  scale 2 

(Test    9^)  Hardness,  needle  penetrometer  at  77°  F,  o 

(Test   9^)   Hardness,  consistometer  at  77°  F 90-120 

(Test   gd)  Susceptibility  index >  100 

(Test  10)     Ductility  at  77°  F o 

(Test  15*)  Fusing-point  (K.  and  S.  method) 230-350°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 270-375°  F. 

(Test  1 6)     Volatile  at  325°  F.,  5  hrs.  (dry  substance)  Less  than  2  per  cent 

Volatile  at  400°  F.,  5  hrs Less  than  4  per  cent 

(Test  19)     Fixed  carbon 20-30  per  cent 

(Test  21)     Soluble  in  carbon  disulfide Usually  greater  than  95  per  cent 

Non-mineral  matter  insoluble Less  than  i  per  cent 

Mineral  matter Usually  less  than  5  per  cent 

(Test  22)     Carbenes ; Less  than  i  .o  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 20-50  per  cent 

(Test  26)     Carbon 80-85  per  cent 

(Test  27)     Hydrogen 7-12  per  cent 

(Test  28)     Sulfur 2-  8  per  cent 

(Test  29)     Nitrogen  and  oxygen Trace  to  2  per  cent 

(Test  33)     Solid  paraffins o-Trace 

(Test  34^)   Sulfonation  residue 80-95  per  cent 

(Test  37*)    Saponifiable  matter Trace 

(Test  39)     Diazo  reaction No 

(Test  40)     Anthraquinone  reaction No 

Glance  pitch  appears  to  be  intermediate  between  the  native 
asphalts  and  grahamite.  It  is  probably  derived  from  a  different 
character  of  petroleum  than  gilsonite,  having  nevertheless  reached 
a  parallel  stage  in  its  metamorphosis,  under  approximately  the  same 
external  conditions. 

NORTH  AMERICA 

WEST  INDIES 

Barbados.  Glance  pitch  was  first  reported  in  1750  by  Griffith 
Hughes,  and  since  1896  has  been  mined  almost  continuously.  De- 
posits occur  in  a  number  of  localities  throughout  the  island,  espe- 
cially in  the  Conset  district,  at  Groves,  Springfield,  St.  Margaret, 
Quinty,  and  Burnt  Hill.  This  asphaltite  has  been  marketed  under 
the  name  of  "manjak,"  which  was  originally  applied  to  the  Barbados 
product,  although  the  name  was  subsequently  associated  with  a 
variety  of  grahamite  mined  in  Trinidad.9  The  deposits  were  first 
worked  on  a  commercial  scale  by  Walter  Merivale  in  1896,  who  also 
accurately  described  the  deposit,  and  the  properties  of  the  mineral. 

Barbados  manjak  contains  a  very  small  percentage  of  sulfur 
(between  0.7  and  0.9  per  cent),  and  about  1-2  per  cent  of  mineral 
matter.  Its  specific  gravity  at  77°  F.  is  in  the  neighborhood  of  no> 


238  ASPHALTITES  X 

fusing-point  320-340°  F.  (K.  and  S.  method),  the  percentage  of 
fixed  carbon  as  reported  by  different  observers  varies  between  25 
and  30  per  cent  and  its  solubility  in  carbon  disulfide  97-98  per 
cent  Near  the  surface,  the  rnanjak  is  hard  and  brittle  with  a  high 
fusing-point,  but  at  the  lower  levels  of  the  mines  it  is  found  softer, 
and  with  a  much  lower  fusing-point,  partaking  of  the  nature  of  an 
asphalt,  rather  than  an  asphaltite,  and  clearly  proving  the  meta- 
morphosis of  one  from  the  other.  It  also  indicates  that  the  manjak 
originated  in  the  lower  strata,  having  been  thrust  upward  in  the 
form  of  a  dyke  (see  also  Trinidad  grahamite). 

It  is  used  largely  for  the  manufacture  of  varnishes  and  japans  on 
account  of  its  high  purity,  gloss,  and  intense  black  color.10 

Santo  Domingo  (Haiti).  A  deposit  of  glance  pitch  similar  to 
the  preceding  has  been  reported  near  Azua  on  the  Bay  of  Ocoa. 
This  has  not  been  developed  commercially,  nor  are  analyses  avail- 
able. 

CUBA 

There  are  numerous  deposits  of  glance  pitch  occurring  through- 
out Cuba,  including  the  following : 

Province  of  Pinar  del  Rio.  Several  mines,  under  the  names 
"Constancia,"  "San  Jose,"  etc.,  occur  in  the  district  of  Mariel,  near 
the  village  of  Banes,  on  both  sides  of  the  Alfene  River,  testing  as 
follows : 

(Test    i)     Color  in  mass Black 

(Test   4)     Fracture Conchoidal 

(Test    5)     Lustre Dull 

(Test    6)     Streak Brownish  black 

(Test   7)     Specific  gravity  at  77°  F i .  29-1 .34 

(Test    90)  Hardness,  Moh's  scale 2-3 

(Test  19)     Fixed  carbon 24.3-27. 8  per  cent 

(Test  21 )     Soluble  in  carbon  disulfide 70-74  per  cent 

Non-mineral  matter  insoluble 2-3  per  cent 

Mineral  matter 24-27  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 37. 5-49.  o  per  cent 

This  glance  pitch  carries  considerable  adventitious  mineral  mat- 
ter, thus  differing  from  the  preceding. 

Province  of  Santa  Clara.  Veins  of  glance  pitch  have  been  re- 
ported in  the  northern  portion  of  Sancti  Spiritus  district,  likewise 
in  Yaguajay  district  along  the  eastern  bank  of  River  Jatibonico  del 
Norte.  The  latter  are  probably  a  continuation  of  the  veins  occurring 
on  the  west  side  of  this  same  river  in  Province  of  Camaguey,  de- 
scribed below. 


X 


GLANCE  PITCH 


239 


Province  of  Camaguey.  In  the  Moron  district,  on  the  west  side 
of  River  Jatibonico  del  Norte,  several  mines  of  glance  pitch  resem- 
bling gilsonite  have  been  developed,  known  as  "Esperanza,"  uSan 
Rafael/'  "Manocal"  and  "Talaren."  The  last  named  is  the 
largest,  and  the  product  is  shipped  from  Port  Tariffa.  The  material 
tests  as  follows: 


Selects 


Seconds 


(Test 
(Test 
(Test 
(Test 
(Test 

I) 
4) 
5) 
6) 
7) 

Color  in  mass  
Fracture  
Lustre  
Streak  
Specific  gravity  at  77°  F  

Black 
Conchoidal 
Bright 

Black 

1.  12 

Black 
Conchoidal 
Bright 
Black 

1.  12 

(Test 

8*) 

Hardness,  Moh's  scale  

2 

2 

(Test 

15*) 

Fusing-point  (K.  and  S.  method)  

315° 

F. 

345 

o 

F. 

(Test 

15*) 

Fusing-point  (R.  and  B.  method)  

284° 

F. 

372 

o 

F. 

(Test 

19) 

Fixed  carbon  

26  per  cent 

28  per  cent 

(Test 

«) 

Soluble  in  carbon  disulfide  

99- 

25  per  cent 

97- 

3 

per 

cent 

Non-mineral  matter  insoluble  

o. 

23  per  cent 

0, 

2 

per  cent 

Mineral  matter  

o. 

52  per  cent 

2. 

5 

per 

cent 

(Test 

22) 

Carbenes  

0. 

i  per  cent 

0, 

2 

per 

cent 

(Test 

23) 

Soluble  in  88°  petroleum  naphtha.  .  .  . 

18. 

o  per  cent 

I4» 

5 

per 

cent 

(Test 

26) 

Carbon  

79- 

7  per  cent 

.  .  . 

. 

(Test 

27) 

Hydrogen  

8. 

2  per  cent 

.  .  . 

. 

(Test 

28) 

Sulfur  

7- 

4  per  cent 

.  .  . 

. 

Undetermined  (nitrogen  and  oxygen)  . 

4- 

8  per  cent 

... 

• 

Total 100.0  per  cent 


MEXICO 


State  of  Vera  Cruz. 


District  of  Chapapote.  As  stated  previously,  deposits  of  very 
pure  asphalt  occur  in  this  locality,  varying  from  very  soft  consist- 
ency to  a  hard  and  brittle  asphaltite,  properly  classified  as  "glance 
pitch."  They  show  a  lustrous  and  conchoidal  fracture,  a  black 
streak,  fuse  in  the  neighborhood  of  250°  F.  (K,  and  S.  method), 
contain  over  20  per  cent  of  fixed  carbon,  and  are  more  than  99  per 
cent  soluble  in  carbon  disulfide. 

District  of  Papantla.  Glance  pitch  occurs  near  the  village  of 
Talaxca,  about  6  miles  north  of  Papantla,  within  30  miles  of  the 
port  of  Gutierrez-Zamora  on  the  Tecolutla  River,  whence  it  is  trans- 
ported by  lighters  to  vessels  at  Tecolutla  on  the  Gulf  of  Mexico. 
The  glance  pitch  fills  a  fissure  in  hard  conglomerate  in  a  vein  2  to  3 
feet  wide,  running  north  and  south  for  a  length  of  about  35  kilo- 


240  ASPHALTITES  X 

meters.     It  has  been  mined  to  a  depth  of  80  feet,  and  tests  as 
follows : 

(Test    i)     Color  in  mass Black 

(Test   4)     Fracture Conchoidal 

(Test   5)    Lustre Bright 

(Test   6)     Streak Black 

(Test   7)     Specific  gravity  at  77°  F i  .093-1 . 108 

(Test  1 5^)  Fusing-point  (R.  and  B.  method) 298-317°  F. 

(Test  19)     Fixed  carbon 21 . 5-24.0  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 99.76  per  cent 

Non-mineral  matter  insoluble 

Mineral  matter o .  24  per  cent 

Total 100 .00  per  cent 

(Test  22)     Soluble  in  carbon  tetrachloride ,    99 . 72  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 27-35  per  cent 

(Test  28)     Sulfur 7. 13  per  cent 

TT    ,  UNITED  STATES 

Utah. 

Emery  County.  Deposits  of  glance  pitch  occur  at  Temple 
mountain,  45  miles  southeast  of  the  town  of  Greenriver  on  the 
eastern  flank  of  San  Rafael  swell,  also  at  Flat  Top  mountain, 
2 1/2  miles  to  the  southeast  Occur  as  glistening  black  nodules  rang- 
ing in  size  up  to  2  J^  in.  in  diameter  in  a  bed  of  sandstone  con- 
glomerate about  60  ft.  thick.  The  asphaltite  is  characterized  by  the 
fact  that  it  carries  uranium  and  vanadium,  which  are  assumed  to 
have  been  incorporated  in  it  during  its  migration  from  the  under- 
lying strata,  thereby  hardening  the  asphaltite  and  "fixing"  it  in  the 
present  associated  rocks.  The  material  contains  an  average  of  1.75 
per  cent  USO8  and  4  per  cent  V2O5.  Specimens  taken  from  the 
Cowboy  claim  (Shinarump  conglomerate),  designated  "A,"  and 
from  the  lower  part  of  sandstone  on  the  west  slope  of  Temple 
mountain,  designated  "B,"  analyze  as  follows: 

Specimen" A?          Specimtn"B" 
Per  cent  Per  cent 

Loss  on  ignition » *  49-57  67 . 1 1 

Ash  soluble  in  HC1: 

Uranium  oxide  (UsOg) i .  13  2.88 

Vanadium  oxide  (V A) 0.23  1.17 

Sulfur 4-98  i  -37 

Arsenic Trace  Trace 

Selenium. I.............  None  None 

Ash  insoluble  in  HC1 4^-3a  *6<$4 

Total -       102*13  99.07 


X  GLANCE  PITCH  241 

In  many  places  the  asphaltite  has  completely  weathered  away/ 
leaving  deposits  of  the  metals  and  metalloids  in  the  form  of  uranium 
and  vanadium  hydroxides,  uranium  vanadate,  calcium  vanadates 
(i.e.,  red  and  green  varieties),  calcium-uranium  vanadate,  potas- 
sium-uranium vanadate,  copper-uranium  arsenate,  etc,1 


11 


CENTRAL  AMERICA  i2 

NICARAGUA 

District  of  Chontales.  A  vein  of  glance  pitch  has  been  reported 
about  10  miles  northeast  of  Santo  Tomas,  northeast  of  the  moun- 
tain range,  about  i  in.  thick,  in  a  fault  plane  of  small  displacement, 
cutting  water-laid  volcanic  tuffa. 

SALVADOR 

Department  of  San  Miguel.  At  the  waterfall  in  Quebrada 
Granda,  one  mile  southwest  of  the  "Otuscal1  Ranch,"  glance  pitch 
is  present  as  a  fracture  filling,  associated  with  calcite  and  chalcedony. 

SOUTH  AMERICA 
COLOMBIA 

Department  of  Tolima.  A  large  deposit  of  glance  pitch  occurs 
at  Chaparral  on  the  Saldana  River,  which  empties  into  the  Magda- 
lena  River.  The  deposit  is  about  100  miles  southwest  of  Bogota. 
It  is  transported  by  boats  down  the  Magdalena  River  to  the  coast, 
whence  it  is  exported.  About  2000  tons  are  shipped  annually 
having  a  high  fusing-point  and  over  99  per  cent  soluble  in  carbon 
disulfide.13  It  is  used  largely  for  the  manufacture  of  varnish  and 
tests  as  follows: 

(Test  4)    Fracture Conchoidal 

(Test    5)    Lustre , .  Bright 

(Test   6)    Streak Black 

(Test   7)    Specific  gravity  at  77°  F i ,  12 

(Test   8a)  Hardness,  Moh's  scale, a 

(Test   8i)  Hardness,  penetrometer o 

(Test  15)    Fusing-point  (K.  and  S.  method) 275°  F. 

(Test  19)    Fixed  carbon , 26,45  per  cent 

(Test  21)    Solubility  in  carbon  disulfide 96,0  per  cent 

Non-mineral  matter  insoluble o.>per  cent 

Mineral  matter 3.3  per  cent 


242  ASPHALTITES  X 

Department  of  Bolivar.  A  similar  deposit  occurs  at  Simiti,  on 
the  western  bank  of  the  Magdalena  River,  north  of  the  foregoing 
deposit 

EUROPE 

GERMANY 

Bentheim.  Deposits  of  asphaltite,  probably  of  the  nature  of 
glance  pitch,  are  found  in  the  vicinity  of  Bentheim,  These  were 
first  regarded  as  a  coal,  and  have  been  worked  since  1732.  The 
material  is  hard,  shows  a  glossy,  conchoidal  fracture,  a  black  streak, 
specific  gravity  of  1,07  to  1.09,  and  0.53  to  11.24  P^r  cent  ash. 


14 


ASIA 

SYRIA  (LEVANT  STATES) 

Vilayet  of  Sham  (Syria).  An  extensive  series  of  glance  pitch 
deposits  occur  in  the  vicinity  of  Hasbaya  (see  map,  Fig.  72)  in  the 
upper  Jordan  valley,  on  the  western  slope  of  Mount  Hermon  (  Jebel 
esh  Sheikh).  The  principal  mine,  known  as  "Suk  el  Chan"  or 
"Bir  el  Hummar"  is  located  on  the  eastern  slope  of  Jebel  ed  Dahr, 
a  hill  separating  the  Jordan  River  (Nahr  Hasbani)  and  the  Nahr 
Litani,  where  a  deposit  of  glance  pitch  of  brownish  black  color  is 
found  in  a  vein  up  to  4  m.  thick.  It  has  a  brilliant  lustre  and  a 
black  streak,  specific  gravity  at  60°  K  of  1.104,  contains  from  a 
trace  to  5  per  cent  mineral  matter,  fuses  at  275°  F.,  and  yields  27 
per  cent  fixed  carbon.  An  average  specimen  on  analysis  shows: 
carbon  77,18  per  cent,  hydrogen  9,07  per  cent,  sulfur  0,40  per 
cent,  nitrogen  2.10  per  cent,  and  mineral  matter  0.50  per  cent. 
This  deposit  is  said  to  have  been  worked  since  about  1600  B.C. 
Some  of  the  ancient  pits  are  still  to  be  seen,  as  deep  as  60  m. 
From  1890  to  1900,  about  66,000  tons  were  mined,  and  a  quantity 
exported  to  the  United  States  for  the  manufacture  of  varnishes,  for 
which  it  is  well  suited.  .  In  this  same  region  there  is,  found  an 
asphaltic  limestone  impregnated  with  an  average  of  10  per  cent 
asphalt  of  comparatively  high  fusing-point  (presumably  glance 
pitch)  associated  with  petrified  fish  remains.15 


X 


GRAHAMITE 


243 


Palestine.  The  Dead  Sea  deposits  are  merely  of  historical  inter- 
est, as  they  constituted  one  of  the  principal  sources  of  supply  of 
asphalt  for  the  ancients.  There  appear  to  be  large  veins  of  asphalt 
at  the  bottom  of  the  Dead  Sea,  the  water  of  which  is  saturated  with 
salt  (25  per  cent  solution)  having  a  gravity  of  about  1.21.  The 
asphalt  has  a  specific  gravity  at  77°  F.  of  1.104,  and  as  masses  be- 
come detached  at  the  bottom  by  earthquake  shocks  or  otherwise, 
they  float  to  the  surface,  where  they  are  gathered  up  by  natives.  A 
section  through  the  Dead  Sea  showing  the  veins  of  asphaltite  is 
illustrated  in  Fig.  81.  Deposits  also  occur  at  Es  Sebba  (Es  Sebbe) 


FIG.  8 1. — Vertical  Section,  through  Dead  Sea  Showing  Glance  Pitch  Veins. 

and  Masada  on  the  west  shore,  and  at  Seil-el-Modschib  on  the  east 
shore  of  the  Dead  Sea.  This  glance  pitch  shows  a  lustrous,  con- 
choidal  fracture,  and  a  black  streak.  Its  fusing-point  is  275°  F., 
over  99  per  cent  is  soluble  in  carbon  disulfide,  and  it  yields  20  per 
cent  of  fixed  carbon.  The  supply  is  limited  and  the  material  is 
used  only  to  a  small  extent  locally.1 


16 


MESOPOTAMIA  (IRAQ) 

A  deposit  occurs  at  Abu  Gir  on  the  Euphrates  River,  west  of 
Baghdad,  containing  86.5  per  cent  soluble  in  carbon  disulfide,  10.0 
per  cent  mineral  matter  and  3.5  per  cent  water;  having  a  fusing- 
point  (R.  and  B.)  of  172°  C.  and  containing  7.3  per  cent  sulfur. 
The  mineral  constitutents  contain  Ca,  Mg  and  Fe,  with  a  trace  of 
vanadium. 

GRAHAMITE 

This  asphaltite  varies  considerably  in  composition  and  physical 
properties,  some  deposits  occurring  fairly  pure  and  others  are  asso- 


244  ASPHAJLTITES  X 

dated  with  considerable  mineral  matter,  running  as  high  as  50 
per  cent17    In  general,  however,  it  complies  with  the  following : 

Test     i)    Color  in  mass Black 

(Test  4)    Fracture Conchoidal  to  hackly 

(Test   5)    Lustre Very  bright  to  dull 

(Test  6)    Streak  on  porcelain Black 

(Test   7)    Specific  gravity  at  77°  P.: 

Pure  varieties  (containing  less  than  10  per 

cent  mineral  matter) 1 . 15-1 .20 

Impure  varieties  (containing  more  than  10 

cent  mineral  matter) 1 . 175-1 .50 

(Test   90)  Hardness,  Moh's  scale 2-3 

(Test   gk)  Hardness,  needle  penetrometer  at  77°  F o 

(Test    9<r)  Hardness,  consistometer  at  77°  F Over  150 

(Test   gel)  Susceptibility  index >  100 

Behavior  on  heating  in  flame: 
Variety  showing  a  conchoidal  fracture  and  a 

black  lustre Decrepitates  violently 

Variety  showing  a  hackly  fracture  and  a 

fairly  bright  to  dull  lustre Softens,  splits  and  burns 

(Test  150)  Fusing-point  (K.  and  S.  method) 350-600°  F. 

(Test  1 5$)  Fusing-point  (R..  and  B.  method) 370-625°  F. 

(Test  1 6)    Volatile  at  500°  F.,  5  hrs Less  than  i  per  cent 

(Test  19)    Fixed  carbon 30~55  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 45-100  per  cent 

Non-mineral  matter  insoluble  in  carbon  disul- 
fide   Less  than  5  per  cent 

Mineral  matter Variable  (up  to  50)  per  cent 

(Test  aa)    Carbenes , 0-80  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha Trace-5o  per  cent 

(Test  30)    Oxygen  in  non-mineral  matter o-a  per  cent 

(Test  33)    Solid  paraffins o-Trace  per  cent 

(Test  34^)  Sulfonation  residue 80-95  per  cent 

(Test  37*)  Saponifiable  matter Trace 

(Test  39)    Diazo  reaction No 

(Test  40)    Anthraquinone  reaction , , . . .  No 

In  general,  grahamite  is  characterized  by  the  following  features : 
i)   High  specific  gravity; 


Black  streak; 

High  f  us  ing-point; 

High  percentage  of  fixed  carbon, 

Solubility  of  non-mineral  matter  in  carbon  disulfide. 


A  process  has  been  proposed  for  reducing  the  fusing-point  of 
grahamite,  by  heating  the  material  either  alone,  or  with  a  propor- 
tion of  serni-asphaltic  residual  oil  (12  to  14°  Baurne)  in  a  closed 
retort  at  400°  F,  for  twenty- four  hours,  under  a  pressure  of  50  Ib. 
per  sq.  in.  This  converts  the  asphaltite  into  a  product  similar  in 


GRAHAMITE 


245 


appearance  to  gilsonite,  having  a  black  streak.  The  percentage  of 
carbenes  is  reduced  and  the  proportion  soluble  in  88°  petroleum 
naphtha  is  increased.18  Processes  have  been  described  for  fluxing 
grahamite  with  coal  tar  19 ;  also  for  fluxing  grahamite  and  adding 
a  mineral  filler.20 

Deposits  of  grahamite  occur  in  the  following  localities: 


NORTH  AMERICA 

UNITED  STATES 


West  Virginia. 


Ritchie  County.     The  original  deposit  of  grahamite  was  dis- 
covered in  West  Virginia.21     It  was  first  described  by  Prof.  J.  P. 


FIG.  82.— View  of  Grahamite  Vein,  Ritchie  County,  West  Virginia. 


246 


ASPHALTITES 


X 


Leslie  in  a  paper  read  before  the  American  Philosophical  Society, 
March  20,  1863.  It  is  found  in  but  a  single  locality  in  Ritchie 
County,  about  25  miles  southeast  of  Parkersburg.  The  grahamite 
fills  an  almost  vertical  fissure  in  sandstone,  a  mile  long,  varying  in 
width  from  2  in.  at  the  ends  to  4  and  5  ft.  in  the  center.  Its  depth 
is  assumed  to  be  1500  to  1600  ft 

The  mine  has  long  been  abandoned,  as  the  available  supply  of 
grahamite  is  exhausted.    Figure  82  shows  a  view  of  the  opening  in 


FtiULTZQNE^ 

M/necf  from  /ot//f 


<\  ,VV\ U!DDERM1Y_ 


'  '  ••  -  ._  ;#/W 

to  the  Ritchie 


„„„„„   rflfrfrr,^,-0 


Elevation 


bewhtre 


A*WA     16'Wide 


f Fissure  above  fault 
I     ?4"W/&      30'M&        3&W& 


*  fissure  be  fort  Faufr 


Plan 


FIG.  83. — Sections  through  Grahamite  Mine,  Ritchie  County,  W.  Va. 

the  hillside  from  which  the  grahamite  has  been  removed.  Figure  83 
shows  the  nature  and  extent  of  the  workings.  Next  to  the  sand- 
stone walls,  the  grahamite  shows  a  coarsely  granular  structure,  with 
a  semi-dull  fracture.  The  following  layer  is  highly  columnar  in 
structure  with  a  lustrous  fracture.  Finally,  in  the  center  of  the 
vein,  the  grahamite  is  more  compact  and  massive,  with  the  col- 
umnar structure  less  developed  and  a  semi-dull  fracture.  This 
variation  in  structure,  fracture  and  lustre  is  characteristic  of  gra- 
hamite deposits. 

On  analysis  it  tests  as  follows: 


X 


GRAHAMITE 


247 


(Test  6) 
(Test  7) 
(Test  90) 

(Test  150) 
(Test  19) 
(Test  21) 


Streak  on  porcelain Black 

Specific  gravity  at  77°  F 1 . 18-1 . 185 

Hardness  on  Moh's  scale 2 

Behavior  on  heating  in  flame Softens,  burns  and  splits 

Fusing-point  (K.  and  S.  method) 520-540°  F. 

Fixed  carbon 42 . 1 5-42 , 48  per  cent 

Soluble  in  carbon  disulfide . .  97. 61  per  cent 

Non-mineral  matter  insoluble 0.17  per  cent 

Combined  mineral  matter o. 44  per  cent 

Free  mineral  matter 1.71  per  cent 


Total 99 . 93  per  cent 

(Test  22)     Insoluble  in  carbon  tetrachloride 55- o    per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 3.0    percent 

(Test  25)    Hydroscopic  moisture 0.07  per  cent 

(Test  26)    Carbon 86. 56  per  cent 

(Test  27)     Hydrogen 8 . 68  per  cent 

(Test  28)     Sulfur i  .79  per  cent 

Difference 2. 97  per  cent 

Texas. 

Fayette  and  Webb  Counties.  Clifford  Richardson 22  reports  a 
deposit  of  grahamite  in  Fayette  County  in  the  neighborhood  of 
Lagrange,  also  an  occurrence  in  Webb  County,  near  Laredo,  in  the 
southern  portion  of  the  State.  These  test  as  follows: 


Fayette  County 
Grahamite, 
Per  Cent. 

Webb  County 
Grahamite, 
Per  Cent. 

(Test  10) 

Fixed  carbon  

37.7 

52.8 

(Test  21  ) 

Mineral  matter  

4.2 

2.O 

(Test  2c) 

Moisture.  

o.  3 

O-3 

(Test  26) 

Carbon  

76.2 

78.6 

(Test  27) 

Hydrogen  

6.6 

7.5 

(Test  28) 

Sulfur    

7.4 

5.4 

(Test  20) 

Nitrogen  

0.4 

1.2 

Undetermined  

<.2 

C.I 

Oklahoma.23 

Pushmataha  County.  Two  small  occurrences  are  reported  in 
the  Potato  Hills  about  5  miles  north  of  Tuskahoma,  One  is  in  SE 
y4,  Sec.  i,  T  2  N  R  19  E,  and  the  other  in  NE  #,  Sec.  2,  T  a 
N,  R  19  E.  Neither  of  these  is  of  importance. 

Jackford  Creek  Deposit.  The  largest  known  grahamite  vein  in 
the  world  occurs  in  Jackf  ork  Valley*  1 2  miles  west  of  Tuskahoma  in 


ASPHAITITES 


X 


the  SE  J4,  NE  M,  Sec.  9,  T  2  N,  R  18  E,  It  is  about  i  mile  long, 
and  varies  in  thickness  from  19  to  a  maxipium  of  25  ft  At  the 
surface,  the  vein  dips  at  an  angle  of  37°,  and  after  continuing  down- 
ward for  140  ft,  turns  suddenly  at  an  angle  between  45  and  50  deg. 
It  is  illustrated  in  Fig.  84.  The  grahamite  fills  a  fault  in  shaly  sand- 
stone. The  upper  wall  of  the  vein  is  firm  and  requires  no  timbering. 
In  mining  the  material,  oive-ins  are  prevented  by  allowing  pillars 
of  grahamite  to  remain  in  place  to  support  the  upper  "hanging" 
rock  wall.  When  the  author  visited  the  mine  in  1912,  a  track  was 
laid  along  the  bottom  wall,  and  the  grahamite  hoisted  out  in  skips  on 


Courtesy  of  Central  Commercial  Co. 
FIG.  84.— Vertical  Section  through  Grahamite  Mine  Near  Tuskahoma,  Okla. 

a  cable-way.  There  is  evidence  of  large  pieces  of  rock  having  be- 
come detached  from  the  hanging  wall  and  fallen  into  the  deposit 
of  grahamite  before  it  became  solid. 

As  is  tfopimon  with  most  grahamite  deposits,  several  distinct 
types  of  material  are  found  in  the  vein.  The  grahamite  which  oc- 
curs atong  the  rock  walls  for  a  thickness  of  2  to  6  ft.  (type  b)  shows 
a  hackly  (known  as  a  "pencillated")  fracture,  and  a  semi-dull  to  dull 
lustre/ whereas  the  grahamite  taken  from  the  center  of  the  vein 
(type  a)  shows  a  conchoidal  fracture  and  very  bright  lustre  similar 
to  gilsonite.  This  is  probably  due  to  the  fact  that  the  grahamite 
in  contact  with  the  wall  cooled  more  rapidly  than  the  central  portion, 


X 


GRAHAMITE 


249 


and  very  likely  has  also  been  subjected  to  more  or  less  strain  from 
movements  of  the  suijounding  rock.  Many  thousand  tons  of  gra- 
hamite  have  been  mined  from  this  vein  which  is  now  pretty  nearly 
exhausted  (from  6000  to  7000  carloads  during  the  first  four  years 
of  its  operation,  and  at  the  time  of  the  author's  visit  about  50  tons' 
per  day).  The  cost  of  moving  to  the  surface  is  comparatively 
small,  but  the  material  has  to  be  carted  10  miles  to  Tuskahoma,  HI* 
nearest  shipping  point. 

On  analysis  the  two  varieties  (a)  and  (b)  test  as  follows: 

(Test   ;)     Color  in  mass  (types  a  and  b) Black 

(Test   4)    Fracture  (type  a) Conchoidal 

Fracture  (type  b) Hackly 

(Test    5)    Lustre  (type  a) .,..,  Bright 

Lustre  (type  b) Semi-bright  to  dull 

(Test   6)    Streak  (types  a  and  b) Black 

(Test   7)    Specific  gravity  at  77°  F.  (types  a  and  b) . .  i .  1 8-1 . 195 

(Test    9* )  Hardness,  Moh's  scale 2 

Behavior  on  heating  in  flame  (type  a) Intumesces  violently 

Behavior  on  heating  in  flame  (type  b) Softens,  splits  and  burns 

(Test  1 5* )  Fusing-point  (K.  and  S.  method)  (types  a  and  b) . .  530-604°  F, 

NOTE. — There  is  no  appreciable  difference  in  fusing-point  between  the  two  varieties 
(a  and  b)* 

(Test  16)    Volatile  matter  500°  F.,  5  hrs Less  than  i  per  cent 

(Test  19)    Fixed  carbon  (types  a  and  b) 52.76-55.00  per  cent 

(Test  21)    Solubility  in  carbon  disulfide Greater  than  99. 5  per  cent 

'    Non-mineral  matter  insoluble Less  than  o,  5  per  cent 

Free  mineral  matter  (types  a  and  b) ...,.,  o.  21-0, 70  per  cent 

32° 77° 115° 


IW 

90 
80 
70 
60 
50 
40 
30 
20 
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A 

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tartness 
ensile  Strength*® 

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Susceptibility  Index*  2t.$ 

\ 

X 

MO 

vl 

\ 

S 

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0 

X 

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45.0 

j\k 

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'-»*• 

10    ZO    W    40    50    eo    70  60    90    100   HO  120   130  140  150  160 
Tempera  ture,Degrees  Fahrenheit 

FIG.  85. — Chart  of  Physical  Characteristics  of  Fluxed  Oklahoma  Grahamite  Mixture. 


250  ASPHALTITES  X 

Figure  85  shows  the  consistometer  hardness,  tensile  strength 
(multiplied  by  10)  and  ductility  curves  of  a  mixture  of  the  graham- 
ite  and  residual  oil,  fluxed  together  so  as  to  have  a  hardness  of 
exactly  25.0  at  77°  F.  (Test  gc),  equivalent  to  a  penetration  at  77° 
F.  of  20  (Test  9&).  The  mixture  contains:  grahamite,  60  per  cent; 
and  residual  oil,  40  per  cent.  The  resulting  fusing-point  (K.  and  S. 
method)  was  277°  F.  The  same  residual  oil  was  used  in  this  test 
as  for  the  gilsonite  in  Fig.  76,  and  the  fusing-point  of  the  grahamite 
used  was  550°  F.  (K.  and  S.  method).24 

Another  mixture  containing  33  per  cent  of  the  grahamite  and 
67  per  cent  of  the  same  residual  oil  tested  as  follows: 

(Test    9^)  Penetration  at  115°  F.,  50  g.,  5  sec 81 

Penetration  at  77°  F.,  100  g.,  5  sec 50 

Penetration  at  32°  F.,  zoo  g.,  60  sec 55 

Penetration  at  o°  F.,  200  g.,  60  sec 29 

(Test   gc)  Consistency  at  1 15°  F 5.8 

Consistency  at  77°  F 11.7 

Consistency  at  32°  F 21 . 5 

Consistency  at  o°  F 37. 6 

(Test    9*0  Susceptibility  index 11.7 

(Test  iob)  Ductility  at  115°  F 15 

Ductility  at  77°  F 3 

Ductility  at  32°  F i  J 

Ductility  at  o°  F , J 

(Test  150)  Fusing-point  (K.  and  S.  method) 135°  F. 

(Test  15*)  Fusing-point  (R.  and  B.  method) 147°  F. 

(Test  16)    Volatile  at  500°  F.,  5  hrs o. 6  per  cent 

(Test  17^)  Flash-point 535°  F. 

This  particular  mixture  is  characterized  by  its  extremely  low 
susceptibility  index  and  its  high  ductility,  which  manifests  itself 
even  at  o°  F. 

Impson  Valley  Deposit.  This  occurs  on  a  branch  of  the  Ten- 
mile  Creek  on  the  SW  J4,  Sec.  21  and  NW  */4,  Sec.  28,  T  i  S., 
R  14  E.,  about  1 6  miles  northwest  of  Antlers.  It  is  known  under 
various  names  such  as  Jumbo  Mine,  Choctaw  Mine,  or  Old  Slope 
Mine,  This  is  the  second  largest  deposit  in  the  State  of  Oklahoma. 

It  occurs  in  a  zone  of  faulting  and  fracture  in  shale  rock,  and  the 
vein  is  lenticular  in  form,  occurring  as  a  series  of  pockets  of  the 
general  form,  illustrated  in  Fig.  32,  varying  in  thickness  from  a 
fraction  of  an  inch  to  30  ft.  as  a  maximum.  As  the  dip  of  the  vein 
is  very  steep,  the  material  must  be  hoisted  out  in  buckets  with  a 
windlass,  and  then  hauled  15  miles  to  Moyer,  the  nearest  shipping 


X  GRAHAM1TE  251 

point.  Heavy  timbering  is  necessary  on  account  of  the  character 
of  the  enclosing  rock.  The  grahamite  shows  the  same  variation  in 
fracture  and  lustre  as  the  Jackford  Creek  deposit.  On  analysis  it 
tests  as  follows: 

Color  in  mass,  fracture,  specific  gravity,  hardness  and  behavior 
on  heating  in  flame,  same  as  the  preceding : 

(Test  15)     Fusing-point  (K.  and  S.  method) 460-520°  F. 

(Test  1 6)    Volatile  matter,  500°  F.,  5  hrs Less  than  I  per  cent 

(Test  19)    Fixed  carbon 48.5-53-0  per  cent 

(Test  21)     Solubility  in  carbon  disulfide 90. 5-96. a  per  cent 

Non-mineral  matter  insoluble 0.0-6.0  per  cent 

Free  mineral  matter 1 . 1-6. 7  per  cent 

(Test  22)     Carbenes 68  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha 0.2-0.7  per  cent 

(Test  25)     Moisture  at  ioo°-C 0.0-0.7  per  cent 

(Test  26)    Carbon 83.90  per  cent 

(Test  27)     Hydrogen 7.14  per  cent 

(Test  28)    Sulfur i  .04-2.24  per  cent 

Undetermined 6,72  per  cent 

(Test  340)  Saturated  hydrocarbons 0.32  per  cent 

Atoka  County.  McGee  Creek  Deposits.  Two  small  veins,  one 
4  in.  and  another  about  i  ft  in  thickness,  occur  in  the  SW  J4,  Sec. 
23,  T  i  N,  R  14  E,  about  15  miles  northwest  of  Antlers.  These 
constitute  the  so-called  "William's  Mine."  Shafts  have  been  sunk 
from  15  to  20  ft,  but  not  sufficient  grahamite  has  been  found  to 
warrant  continuing  operations.  It  tests  as  follows: 

(Test  19)    Fixed  carbon 43. 5-45.7  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 95-7~99-7  per  cent 

Non-mineral  matter  insoluble 0.0-4.0  per  cent 

Free  mineral  matter 0.3  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 4. 5-  6. 8  per  cent 

A  larger  deposit  also  occurs  in  the  vicinity  of  McGee  Creek,  in 
the  NE  }4,  Sec.  25,  T  i  S,  R  13  E,  and  NW  *4,  Sec.  30,  T  i  S, 
R  14  E,  about  12  miles  southeast  of  Stringtown.  This  is  known 
as  the  Pumroy  or  Moulton  Mine.  The  grahamite  fills  a  fissure, 
caused  by  faulting,  and  is  reported  to  be  14  to  15  ft.  thick  at  the 
surface,  tapering  to  about  4  ft  at  a  depth  of  no  ft.  The  mine 
is  now  abandoned,  but  when  operated  some  years  ago,  about  2000 
tons  were  mined  annually,  being  hauled  1 5  miles  to  Stringtown,  the 
nearest  shipping  point  A  prospect  occurs  about  %  niile  south  of 


252  ASPHALTITES  X 

the  foregoing,  consisting  of  a  vein  about  2  ft.  thick.    On  analysis 
it  tests  as  follows : 

(Test  151?)  Fusing-point  (K.  and  S.  method) 473°  F. 

(Test  19)    Fixed  carbon 38.42-41 .o  per  cent 

(Test  21)    Solubility  in  carbon  disulfide 83 . 7  -95 . o  per  cent 

Non-mineral  matter  insoluble 4.8-9,2  per  cent 

Free  mineral  matter 0.98-  7.1  per  cent 

Boggy  Creek  Deposit.  This  occurs  about  6  miles  northeast  of 
Atoka,  and  i  mile  from  the  M.  K.  &  T.  R.  R.  in  the  SW  %,  Sec.  29, 
T  i  S,  R  1 2  E.  The  vein  occurs  in  shale  varying  in  thickness  from 
several  inches  to  several  feet.  It  has  long  been  abandoned,  and  no 
analyses  are  available. 

Chickasaw  Creek  Deposit.  An  undeveloped  vein  in  shale, 
carrying  streaks  of  grahamite,  about  9  ft.  thick  has  been  reported  in 
Sec,  15,  T  i  S,  R  12  E  about  2l/2  miles  east  of  Stringtown  on  the 
M.  K.  &  T.  Railroad. 

Stephens  County.  This  occurs  in  the  NW  >£,  Sec.  6,  T  2  S, 
R  4  W,  about  6  miles  north  of  Loco,  and  18  miles  east  of  Coman- 
che.  This  vein  has  been  prospected  for  about  half  a  mile,  and  occurs 
as  a  fault  in  sandstone  and  shale.  The  vein  is  of  a  pronounced  len- 
ticular type  existing  in  a  series  of  pockets,  some  as  large  as  10  ft. 
across,  often  connected  with  a  thin  vein-like  crack  less  than  an  inch 
wide.  At  several  points  the  deposit  pinches  out  entirely.  In  the 
direction  of  the  vein,  the  pockets  measure  25  to  100  ft.  horizon- 
tally and  vertically.  A  characteristic  feature  of  this  deposit  is  the 
infiltration  of  pyrites,  grains  of  which  are  clearly  visible  to  the  naked 
eye.  The  surrounding  shale  is  porous,  and  carries  minute  particles 
of  the  grahamite,  which  are  disseminated  throughout  the  rock  for 
some  distance  on  both  sides  of  the  vein.25 

The  material  tests  as  follows: 

(Test  4)    Fracture Hackly 

(Test   5)    Lustre Dull 

(Test   6)    Streak Black 

(Test  i$a)  Fusing-point  (K.  and  S.  method) 401-466°  F. 

(Test  19)    Fixed  carbon 34.4  -39.4  "  per  cent 

(Test  ai)    Soluble  in  carbon  disulfide 81 . 85-97 . 70  per  cent 

Non-mineral  matter  insoluble o .  10-  3 . 60  per  cent 

Free  mineral  matter  (mostly  pyrites) i .  20-14  •  55  per  cent 

Colorado. 

Grand  County.  Deposits  of  grahamite  are  found  in  Middle 
Park  along  the  continental  divide  in  the  northern  part  of  Grand 


X  GRAHAMITE  253 

County.  A  large  vein  occurs  in  Sec.  24,  T  4  N,  R  77  W,  on  a  fork 
of  Willow  Creek  about  25  miles  north  of  Grand  River,  in  a  region 
of  clay,  conglomerate  and  sandstone.  Several  veins  and  fissures 
have  been  prospected,  the  main  vein  varying  in  width  from  2  in.  up 
to  6  ft,  and  extending  100  to  125  ft.  Comparatively  small  quan- 
tities of  the  grahamite  have  been  mined,  due  to  difficulties  in  trans- 
portation to  the  nearest  railroad.  The  product  tests: 

(Test   7)    Specific  gravity  at  77°  F i , 15-1 > 16 

(Test  19)     Fixed  carbon 47-4  -49-3  per  cent 

(Test  21)     Soluble  in  carbon  disuifide 98 . 2  -99 . 3  per  cent 

Non-mineral  matter  insoluble 0.6-1.7  per  cent 

Free  mineral  matter o.o  -  o.  i  per  cent 

(Test  22)     Carbenes 80.6  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha o. 8  -  i  .3  per  cent 

(Test  26)     Carbon 85.9  -86.  i  per  cent 

(Test  27)    Hydrogen 7.63-  7-75  per  cent 

(Test  28)     Sulfur 0.93-  0.99  per  cent 

Undetermined 5-34-  5-45  per  cent 

«  r  TT          r*  MEXICO 

State  of  Vera  Cruz. 

District  of  Papantla.  Grahamite  deposits  occur  about  20  miles 
south  of  Papantla,  near  the  village  of  Espinal,  forming  a  continua- 
tion of  the  glance  pitch  vein  at  the  village  of  Talaxca  (about  6  miles 
north  of  Papantla),  previously  referred  to  herein*  A  total  of  5 
grahamite  veins  have  been  located,  with  outcroppings  at  the  sur- 
face, the  widest  of  which  measures  1.5  meters,  with  an  average 
length  of  700  meters.  The  asphaltite  varies  from  a  true  grahamite 
(A)  to  a  metamorphized  type  (B)  approaching  impsonite,  testing 
as  follows: 

Type"A"  Type"B" 

(Grahamite)  (Impsonite) 

(Test    i)    Color  in  mass Black  Black 

(Test   4)    Fracture Hackly  Hackly 

(Test   5)    Lustre Bright  Dull 

(Test   6)    Streak Black  Black 

(Test   7)    Specific  gravity  at  77°  F 1.15  1.19 

(Test  15*)  Fusing-point  (R.  &  B.) 375°  F.  Decomposes 

(Test  19)    Fixed  carbon 37 -o  per  cent  43-35  per  cent 

(Test  2i)     Soluble  in  carbon  disulfide 99. 80  per  cent  20.00  per  cent 

Non-mineral  matter  insoluble o. ia  per  cent  79 .41  per  cent 

Mineral  matter o .  14  per  cent  o.  59  per  cent 

Total 100.00  per  cent  100.00  per  cent 

(Test  22)    Soluble  in  carbon  tetrachloride 10,3   percent 

(Test  23)    Soluble  in  88°  petroleum  naphtha .     39 . 7  per  cent  3.5    per  cent 

(Test  28)    Sulfur 6. 16  per  cent 


254  ASPHALTITES  X 

State  of  San  Luis  Potosi. 

District  of  Tamazunchale.  A  vein  of  grahamite  has  been  found 
at  Huasteca  on  the  Panuco  River 2e  in  a  vertical  fissure,  occurring  in 
shales  as  an  overflow  at  the  junction  of  the  shale  stratum  with  the 
overlying  sandstone.  On  analysis  the  material  tests  as  follows : 

(Test   4)    Fracture Semi-conchoidal 

(Test    5)    Lustre Bright 

(Test   6)    Streak Black 

(Test   7)    Specific  gravity,  at  77°  F 1.145 

(Test  19)    Fixed  carbon 35.3  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 93 . 8  per  cent 

Non-mineral  matter  insoluble 3.4  per  cent 

Free  mineral  matter 2.8  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha 8.4  per  cent 

(Test  26)     Carbon 77.67  to  83. 14  per  cent 

(Test  27)    Hydrogen 8 .06  to    8 .09  per  cent 

(Test  28)    Sulfur 7.51  to    5. 47  per  cent 

State  of  Tamaulipas.  Another  deposit  has  been  reported  near 
the  City  of  Victoria,  containing  3.4  per  cent  of  non-mineral  matter 
insoluble  in  carbon  disulfide  and  54  per  cent  of  fixed  carbon, 

CUBA27 

Province  Pinar  del  Rio.  In  the  District  of  Mariel,  near  the  City 
of  Bahia  Honda,  there  occurs  a  fairly  large  vein  of  grahamite, 
known  as  "La  America  Mine,"  or  the  "Rodas  Conception  Mine/' 
testing  as  follows  : 

(Test   4)    Fracture Shows  distinct  cleavage  veins 

(Test    5)    Lustre Semi-dull 

(Test   7)    Specific  gravity,  at  77°  F i .  1 57 

(Test  19)    Fixed  carbon 40.0-42 . 2  per  cent 

(Test  ai)    Soluble  in  carbon  disulfide 99.4-99.6  per  cent 

Non-mineral  matter  insoluble o.o-  o.  i  per  cent 

Free  mineral  matter 0.4-  o.  5  per  cent 

(Test  22)    Carbenes About  25  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha..  17.4-20.0  per  cent 

A  smaller  deposit,  known  as  "Santa  Julia/'  occurs  near  the 
stream  of  Don  Hermanos,  7  miles  southwest  of  Bahia  Honda. 

Another  deposit  occurs  near  the  City  of  Mariel,  i  mile  south 
of  Mariel  Bay,  known  as  the  "Magdalena  Mine/'  which  extends 
about  100  ft*  in  length  and  40  ft.  in  width.  The  first  concession  was 
granted  in  1859  involving  3705  acres.  The  veins  consist  of  a  series 
.of  lenses  from  2  to  over  30  meters  wide,  in  calcareous  rock.  The 


X  GJMHAM1TE  255 

deposit  has  been  worked  to  a  depth  of  about  300  feet  Large 
quantities  of  grahamite  of  a  fairly  uniform  composition  have  been 
mined,  characterized  by  the  presence  of  about  40  per  cent  of  asso- 
ciated mineral  matter,  which  has  been  utilized  principally  as  a  com- 
ponent of  paving  compositions.28  It  tests  as  follows : 

(Test   4)    Fracture Conchoidal 

(Test    5)    Lustre Dull 

(Test   6)    Streak Black 

(Test    7)     Specific  gravity  at  77°  F i  .45  to  1 ,49 

(Test  15^)  Fusing-point  (R.  and  B.  method) 374-400°  F. 

(Test  16)     Volatile  at  212°  F About  5% 

(Test  17^)  Flash-point  (open  cup) 41 5-425°  F. 

(Test  19)     Fixed  carbon 30.0-38  .o  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 51     -58  per  cent 

Non-mineral  matter  insoluble 3    -7  per  cent 

Free  mineral  matter 38    -42  per  cent 

(Test  22)     Carbenes i . 5-  6.3  per  cent 

,    (Test  23)     Solubility  in  88°  petroleum  naphtha 37    -48  per  cent 

(Test  26)     Carbon 7*-5-77.8  per  cent 

(Test  27)     Hydrogen 8.5-  8 .7  per  cent 

(Test  28)     Sulfur ! 6.9-  7.7  per  cent 

Difference 6.6-11 .4  per  cent 

Another  vein  occurs  in  this  same  locality,  probably  a  continuation 
of  the  preceding,  known  as  the  "Mercedes  Mine,"  testing  similarly. 

Province  of  Havana.  In  the  neighborhood  of  Campo  Florida, 
grahamite  has  been  obtained  from  a  mine  known  as  "La  Habana," 
which  tests  : 

(Test    4)     Fracture Semi-conchoidal 

(Test    5)    Lustre Dull 

(Test    6)     Streak Black 

(Test    7)     Specific  gravity  at  77°  F i ,  175 

(Test  19)     Fixed  carbon 45.0  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 98 . 9  per  cent 

Non-mineral  matter  insoluble o. 7  per  cent 

Free  mineral  matter 0.4  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha 6.0  per  cent 

(Test  26)     Carbon 82, 5  per  cent 

(Test  27)    Hydrogen 7-  5  per  cent 

(Test  28)     Sulfur 6.4  per  cent 

Undetermined 3 . 6  per  cent 

A  similar  deposit  has  been  reported  about  12  miles  east  of 
Havana  and  another  one,  known  as  the  "Casitalidad  Mine,"  situ- 
ated about  9-10  miles  east  of  Havana,  and  2  miles  south  of  the 
coast,  in  a  vein  600-900  ft.  long  and  1-30  ft  thick,  testing  sub- 
stantially the  same  as  the  preceding. 


256  ASPHALT1TES  X 

Province  of  Santa  Clara*  Nine  miles  northeast  of  the  City  of 
Santa  Clara  near  Loma  Cruz,  there  occurs  the  deposit  known  as 
"Santa  Eloisa,"  in  a  bed  of  serpentine.  It  tests  as  follows: 

(Test    4)    Fracture Semi-conchoidal 

(Test    5)    Lustre Bright 

(Test    6)    Streak Black 

(Test    7)     Specific  gravity  at  77°  F 1.29 

(Test  19)    Fixed  carbon 34~35  P<*  cent 

(Test  21)     Soluble  in  carbon  disulfide 78~79  per  cent 

Non-mineral  matter  insoluble i .  8-2 . 2  per  cent 

Free  mineral  matter 19-20  per  cent 

(Test  22)    Carbenes 2-3  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha. , 31-33  per  cent 

Another  mine  occurs  a  short  distance  from  Placetas  del  Sur,  in 
an  irregular  vein  of  lenticular  form,  occurring  in  several  branches. 
This  mine  is  known  as  the  "Esperanza,"  and  the  product  is  charac- 
terized by  its  comparatively  low  fuslng-point  The  average  ma- 
terial as  mined  tests  as  follows : 

(Test    4)     Fracture Hackly 

(Test    5)    Lustre Moderately  bright 

(Test   6)    Streak Black 

(Test    7)     Specific  gravity,  at  77°  F 1.22 

(Test    go)  Hardness,  Moh's  scale 2 

In  flame Softens,  splits  and  burns 

(Test  150)  Fusing-point  (K.  and  S.  method) 400-433°  F. 

(Test  19)     Fixed  carbon 52, 95  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 97  •  9~98 . 8  per  cent 

Non-mineral  matter  insoluble 0.05-0. 92  per  cent 

Free  mineral  matter i  .15-2.75  per  cent 

Mineral  matter  combined  with  non-mineral 
constituents 0,37  per  cent 


SOUTH  AMERICA 

TRINIDAD 

Two  deposits  of  grahamite  29  occur  near  San  Fernando  on  the 
west  coast  of  the  island  on  the  shore  of  the  Gulf  of  Paria,  known  as 
the  Vistabella  and  Marbella  Mines.  The  grahamite  has  been  mar- 
keted under  the  name  of  "manjak,"  presumably  taking  advantage 
bf  the  popularity  of  the  Barbados  glance  pitch,  although  from  a 
geological  standpoint  the  two  minerals  are  entirely  different  The 
veins  occur  in  soft  shale  and  sandstone,  in  a  region  carrying  petro- 
leum in  considerable  quantities. 


X  GRAHAMITE  257 

A  nufnber  of  veins  of  grahamite  have  been  uncovered,  the  lar- 
gest known  as  the  Vistabella  mine,  which  measures  360  ft  horizon- 
tally and  has  been  mined  to  a  depth  of  about  250  ft  Its  thickness 
is  1 1  ft,  at  the  outcrop,  and  increases  steadily  to  33  ft  at  a  depth 
of  200  ft  Three  distinct  types  have  been  found  in  the  vein,  viz: 

1 I )  An  amorphous  coaly  type  which  has  a  hackly  fracture,  and 
usually  occurs  at  the  margin  of  the  vein.     It  is  dull  in  lustre  and 
exhibits  no  regular  jointings, 

(2)  A  columnar  type,  of  dull  lustre,  having  a  columnar  jointing 
running  at  right  angles  to  the  margins  of  the  vein.    The  jointing  is 
often  well  formed,  dividing  the  material  into  hexagonal  or  pentag- 
onal prisms. 

(3)  A  lustrous  variety  identical  in  appearance  to  gilsonite  and 
Barbados  glance  pitch  (manjak).     This  has  a  bright  lustre,  and  a 
conchoidal  fracture,  being  found  in  the  deeper  workings  of  the  mine, 
at  the  center  of  the  vein. 

There  is  no  chemical  difference  in  the  varieties,  although  it  ap- 
pears that  at  the  center  of*the  vein,  at  a  depth  of  about  120  ft 
the  grahamite  has  a  lower  fusing-point,  closely  resembling  the  Bar- 
bados glance  pitch,  thus  serving  as  a  link  between  the  grahamite 
and  the  glance  pitch,  clearly  proving  that  both  are  derived  by 
metamorphosis  from  a  common  source. 

A  stratum  of  oil-bearing  sandstone  is  known  to  exist  beneath  the 
grahamite,  which  appears  more  than  likely  to  have  been  derived 
from  an  asphaltic  petroleum  which  intruded  under  pressure  through 
a  fault  in  the  shale. 

The  mining  of  the  grahamite  is  comparatively  simple,  but  the 
shafts  have  to  be  carefully  timbered,  and  precautions  have  to  be 
taken  to  avoid  igniting  the  gases  generated  in  the  workings,  as  these 
are  highly  explosive.  Formerly  between  2000  and  2500  tons  were 
mined  per  annum. 

On  analysis  it  tests  as  follows: 

(Test   i)    Color  in  mass Black 

(Test   2)    Homogeneity 3  distinct  types  recog- 
nizable (see  above) 

(Test   4)    Fracture Types  I  and  2,  hackly; 

Type  3  conchoidal. 

(Test   5)    Lustre Types    I    and   2   dull; 

Type  3  bright 

(Test   6)    Streak,.... Black 

(Test   7)    Specific  gravity,  at  77°  F 1.170-1.175 


258 


ASPHALT1TES 


X 


(Test   ga)  Hardness,  Moh's  scale 2 

(Test   9^)  Hardness,  penetrometer o 

On  heating  in  flame Softens,  splits  and  burns 

(Test  ija)  Fusing-point  (K.  and  S.  method) 350-438°  F. 

NOTE.    The  material  resembling  glance  pitch  obtained  from  the  centre  of  the  vein  at 
the  2oo-ft.  level  fused  at  280°  F.  (K.  and  S.  method)* 

(Test  15^)  Fusing-point  (B.  and  R.  method) 370-460°  F. 

(Test  19)    Fixed  carbon 31 .5-35.0  per  cent 

(Test  21)     Solubility  in  carbon  disulfide 91 .7-96.0  per  cent 

Non-mineral  matter  insoluble 0.9-  1.2  per  cent 

Free  mineral  matter 4.0-  6.4,  averaging 

about  5 . 7  per  cent 
Mineral  matter  combined  with  non-mineral 

constituents 1.15  per  cent 

(Test  22)    Carbenes About  40  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha: 

At  loo-ft.  level 12 . 8  per  cent 

At  I40-ft.  level 15. 2  per  cent 

At  200-ft.  level 18. 5  per  cent 

At  2OO-ft.  level,  softer  material  in  center .  56 .  o  per  cent 

(Test  25)    Moisture 0.2-1  .o  per  cent 

(Test  26)     Carbon 84 .o  per  cent 

(Test  27)    Hydrogen 5.7  per  cent 

(Test  28)     Sulfur ! 3-0-3.8  per  cent 

(Test  29)    Nitrogen 2. 2  per  cent 

Figure  86  shows  the  hardness,  tensile  strength  (multiplied  by 
10)  and  ductility  curves  of  a  mixture  of  the  grahamite  fusing  at 
400°  F  (K,  and  S.  method)  and  residual  oil  (the  same  as  utilized 
in  mixture  shown  in  Fig  85,)  fluxed  together  in  such  proportions 

770       ,  ,,5o 


too 

90 
60 
70 
60 
50 


'  Hardness 

— Tensile  Strength*  10 


<S>  Fusing  Point  »277°yf 
Susceptibility  fndex*/2A 


.0     10  »>  30    40    50   60    70   60    90    100   110   120  130  140  150  160 
Temperature.Oegrees  Fahrenheit 

FIG.  $6.— Chart  of  Physical  Characteristics  of  Fluxed  Trinidad  Grahamite  Mixture. 


X  GRAHAM1TE  259 

that  the  hardness  at  77°  F.  is  exactly  25.0  (Test  gc),  correspond- 
ing to  a  penetration  at  77°  F.  of  20  (Test  gb).  The  resulting  mix- 
ture contained  grahamite,  32  per  cent  and  residual  oil,  68  per  cent, 
and  had  a  fusing-point  of  200°  F,  (K.  and  S.  method). 

The  Marbella  vein  is  smaller  than  the  Vistabella,  attaining  a 
thickness  of  7  ft.  near  its  center.  It  is  lenticular  in  form  and  splits 
up  into  two  smaller  veins  at  one  end.  The  grahamite  mined  from 
the  Marbella  vein  has  substantially  the  same  characteristics  as  the 
preceding.  At  the  5o-foot  level,  8.8  per  cent  is  soluble  in  88° 
petroleum  naphtha  (Test  23) ;  at  the  125-ft.  level,  9.6  per  cent;  and 
at  the  200- ft.  level  12  per  cent. 

ARGENTINA 

Province  of  Mendoza.  Asphaltite  (presumably  grahamite?) 
occurs  in  several  localities,  containing  up  to  0.6  per  cent  ash  carrying 
38  per  cent  vanadium  oxide  (V2O5).30 

Province  of  Neuquen.  An  unusual  variety  of  grahamite  occurs 
on  the  eastern  slope  of  the  Andes  Mountains,  in  the  form  of  a  ver- 
tical vein  about  8  km.  long  and  2  to  3  m.  wide.  It  must  be  hauled 
to  the  Great  Southern  Railroad,  whence  it  may  be  transported  to 
the  nearest  port,  Bahia  Blanca.  An  average  sample  tests  as  follows : 

(Test    i)     Color  in  mass Black 

(Test   4)     Fracture Conchoidal 

(Test    5)    Lustre Bright 

(Test   6)    Streak Black 

(Test    7)    Specific  gravity  at  77°  F i .  135 

(Test  15^)  Fusing-point  (K.  and  S.  method) About  625°  F. 

Behavior  on  heating  in  flame Decrepitates  violently 

(Test  21)    Soluble  in  carbon  disulfide 53-35  per  cent 

Non-mineral  matter  insoluble 46.40  per  cent 

Mineral  matter o.  25  per  cent 

Total 100.00  per  cent 

This  asphaltite  fluxes  with  great  difficulty  with  residual  oils  de- 
rived from  asphaltic  and  semi-asphaltic  petroleums,  which  necessi- 
tates the  mixture  being  heated  to  500°  F.  for  several  hours.  During 
this  treatment,  the  "non-mineral  matter  insoluble"  undergoes  depoly- 
merization,  until  it  all  eventually  goes  into  solution.  On  the  other 
hand,  it  fluxes  quite  readily  with  linseed  oil  on  heating  to  500°  F, 
This  grahamite  is  unusual,  in  that  although  half  is  insoluble  in 


ASPHALTJTES  X 

carbon  disulfide,  yet  it  may  be  fluxed  completely  as  described.    It  is 
apparently  on  the  border  line  between  true  grahamite  and  impsonite. 

PERU 
Province  of  Tarma. 

Department  of  Junin.  Deposits  of  grahamite  occur  near  Huari, 
a  small  town  in  the  Department  of  Junin,  a  few  miles  west  of  the 
southern  branch  of  the  Central  Railway  of  Peru,  at  altitudes  of 
15,000  to  16,000  ft.  in  the  Andes  Mountains.  They  occur  as  len- 
ticular veins  in  limestone,  and  are  characterized  by  the  mineral  con- 


FIG.  87. — Map  of  Grahamite  Region  in  Peru. 


stituents  carrying  vanadium  compounds,  probably  in  the  form  of 
sulfide.  The  region  is  illustrated  in  Fig.  87,  and  includes  the  fol- 
lowing mines:  The  Chiucho  mine  consists  of  a  vein  6  in.  to  35  ft. 
wide,  15  miles  from  the  railway,  averaging:  moisture  2.35  per  cent, 
volatiles  40.45  per  cent,  fixed  carbon  55,0  per  cent,  and  ash  2.20 
per  cent  containing  i.o  to  2.25  per  cent  vanadic  oxide  (VaO«).  La 


X  GRAHAM1TE  261 

Lucha  mine  is  connected  with  the  railroad  by  a  small  tramway  5 
miles  long.  The  output  has  been  utilized  extensively  as  a  fuel  by 
the  neighboring  smelters,  and  contains:  moisture  1.15  per  cent,  fixed 
carbon  44.48  per  cent,  volatiles  48.65  per  cent,  and  ash  5.72  per 
cent  carrying  less  than  i  per  cent  vanadic  oxide.  It  is  assumed  that 
the  vanadium  must  have  been  present  originally  in  the  asphaltic 
petroleum  from  which  the  grahamite  was  derived,  since  it  is  not 
found  in  the  associated  rocks.  In  substantiation  of  this  hypothesis, 
it  is  pointed  out  that  vanadium  is  similarly  associated  (up  to  i  per 
cent)  with  certain  black  carbonaceous  shales  in  the  province  of 
Jauja,  some  distance  from  the  foregoing  deposits.31 

Other  occurrences  have  been  reported  at  Minasragra,  near 
Cerro  de  Pasco,  also  at  Lacsacocha  (Yauli),  both  of  which  con- 
tain vanadium. 


CHAPTER  XI 


ASPHALTIC  PYROBITUMENS  * 

The  asphaltic  pyrobitumens  are  natural  substances  composed 
of  hydrocarbons,  characterized  by  their  infusibility  and  comparative 
freedom  from  oxygenated  substances.  They  are  grouped  into  five 
classes,  viz. :  elaterite,  wurtzilite,  albertite,  impsonite,  and  asphaltic 
pyrobituminous  shales.  The  first  four  are  comparatively  free  from 
associated  mineral  matter  (usually  under  10  per  cent).  If  the  min- 
eral matter  predominates,  the  material  is  known  as  an  asphaltic 
pyrobituminous  shale,  which  term  is  applied  indiscriminately  to 
shales  containing  wurtzilite,  albertite  or  impsonite. 

Much  confusion  exists  regarding  the  classification  of  asphaltic 
pyrobitumens.  Every  now  and  then  it  is  alleged  that  some  new 
type  is  discovered,  which  on  closer  investigation  proves  to  be  an  old 
substance  christened  under  a  different  name.  Thus  the  so-called 
"nigrite"  described  by  G.  H.  Eldridge 2  is  nothing  more  than 
albertite. 

Elaterite,  wurtzilite,  albertite  and  impsonite  when  they  occur 
associated  with  less  than  10  per  cent  of  mineral  matter,  are  distin- 
guished from  one  another  as  follows: 


Streak 

Specific  Gravity 
at  77°  P. 

Fixed  Carbon, 
Per  Cent 

Elaterite  

Light  brown 

O.QO—  I  .(X 

2-< 

Wurtzilite  

Light  brown 

I   (X—  I    O7 

*  j 
C—  2C 

Albertite  

Brown  to  black 

i  07—1  10 

>    *j 

2C—  <O 

Impsonite  

Black 

i.  10-1  .25 

•*j    jw 
CO-QO 

All  four  are  derived  from  the  metamorphosis  of  petroleum,  and 
it  is  probable  that  the  impsonite  represents  the  final  stage  of  trans- 
formation of  elaterite,  wurtzilite  and  albertite,  as  well  as  the  as- 
phaltites  (gilsonite,  glance  pitch  and  grahamite). 

262 


XI  ELATER1TE  263 

ELATERITE 

This  asphaltic  pyrobitumen  is  the  prototype  of  wurtzilite.  It  is 
found  in  a  few  localities,  in  small  amounts  and  is  of  scientific  in- 
terest only* 

ENGLAND 

Derbyshire  County.  Elaterite  was  originally  discovered  at  the 
Odin  Mine  in  Castleton  by  M.  Lister  in  i673-4.s  It  was  again 
described  by  C.  Hatchett,4  who  found  it  to  be  moderately  soft  and 
elastic,  like  India  rubber,  having  a  specific  gravity  of  0.953— 0.9 §8. 
It  is  slightly  soluble  in  ether  (18  per  cent)  and  swells  up  in  petro- 
leum naphtha.  H.  J.  Klaproth 5  examined  this  same  material,  stat- 
ing that  it  " fuses  at  a  high  heat,  and  after  this  may  be  drawn  into 
threads  between  the  fingers,"  also  that  it  contains  between  6  and  7 
per  cent  of  ash.6 

AUSTRALIA 
State  of  South  Australia. 

Coorong  District.  A  variety  of  elaterite  is  found  on  the  coast 
south  of  Adelaide,  Australia,  known  under  the  name  of  "coorong- 
ite."  7  It  is  a  rubbery  product,  known  as  "Australian  caoutchouc, " 
which  shows:  fixed  carbon  i  per  cent,  volatiles  97  per  cent,  and  ash 
2  per  cent.  It  was  deposited  on  the  ground  after  the  subsidence  of 
the  floods  in  1865  and  again  in  1920.  It  is  contended  that  coorong- 
ite  is  derived  from  algae-like  organisms,  similar  to  those  which  are 
still  to  be  found  in  certain  salt  lakes  in  South  Australia.  These  or- 
ganisms appear  on  the  lakes  in  winter  and  are  blown  ashore,  where 
they  are  supposed  to  consolidate  into  coorongite. 

ASIATIC  RUSSIA 

State  of  Turkestan.    A  deposit  occurs  at  the  mouth  of  the  Hi 
River,  in  the  neighborhood  of  Lake  Balkash,8  and  tests  as  follows : 

(Test    7)     Specific  gravity 0.995 

(Test  21)    Solubility  in  carbon  disulfide Very  slight 

Free  mineral  matter 3-5  per  cent 

(Test  370)  Acid  value 4.9 

(Test  37^)  Saponification  value 56 . 9 

(Test  37*)  Saponifiable  matter 1 1 .  t  per  cent 

Unsaponifiable  matter 88 .9  per  cent 

It  is  characterized  by  the  presence  of  saponifiable  matter,  and 
in  this  respect  differs  from  the  foregoing.  A  similar  deposit  occurs 


264 


ASPHALT1C  PYROBITUMENS 


XI 


along  Lake  Ala-Kool  (Ala-Kul),  east  of  the  foregoing,  in  masses 
2-10  ft.  wide  and  up  to  2  in.  thick,  associated  with  algae.9 


WURTZILITE 
This  has  been  found  in  but  one  region,10  as  follows : 


Utah. 


UNITED  STATES 


Uinta  County.  This  region  embraces  about  100  square  miles  in 
the  neighborhood  of  Indian,  Lake,  Avintequin  and  Sams  Canyons, 
tributaries  of  Strawberry  Creek,  which  in  turn  leads  into  the  Uinta 

River.  The  veins  occur  about  50  miles 
southwest  of  Fort  Duchesne,  varying 
in  length  from  several  hundred  feet 
to  about  3  miles,  and  from  i  to  22  in. 
wide,  filling  vertical  faults  in  shaly 
limestone.  Altogether  about  30  veins 
have  been  discovered,  closely  resem- 
bling those  of  gilsonite.  Many  of 
them  split  into  a  number  of  smaller 
branches,  either  in  a  vertical  or  hori- 
zontal direction.  The  largest  veins 
occur  between  the  Left-Hand  and  the 
Right-Hand  forks  of  Indian  Canyon. 
Wurtzilite  has  been  exploited  under 
various  names,  including  elaterite 
(improper  use  of  this  name),  aeger- 
ite,  aconite,  etc. 

A  view  of  one  of  the  veins  is 
shown  in  Fig.  88;  a  section  through 
the  mine,  in  Fig.  89;  and  the  tram- 
way for  conveying  the  product  from 
the  hillside  mine  to  the  valley  below, 
in  Fig.  90. 

Wurtzilite  is  characterized  by  being  sectile  and  cutting  like  horn 
or  whalebone.  Thin  flakes  are  somewhat  elastic,  comparable  in  a 
way  to  that  of  glass  or  mica,  rather  than  to  the  yielding  elasticity 
of  rubber.  If  a  shaving  is  bent  too  far  or  suddenly,  it  snaps  off  like 


Courtesy  of  Raven  Mining  Co. 

FIG.    88. — View    of    Wurtzrlite 
Mine,  Uinta  County,  Utah. 


XI 


WURTZ1UTE 


265 


Courtesy  of  Raven  Mining  Co. 
FIG.  89.— Vertical  Section  through  Wurtzilite  Vein,  Uinta  County,  Utah. 


Courtesy  of  Kaven  Mining  Co, 
Fia  90.— Transporting  Wurtzilite  from  the  Mine. 


266  ASPHALTIC  PYROBITUMENS  XI 

glass.  This  distinguishes  it  from  other  asphaltic  pyrobitumens  as 
well  as  the  asphaltite^s.  Attempts  were  made  to  find  its  fusing-point 
by  heating  it  as  high  as  800°  F.  in  sulfur,  but  without  having  any 
effect. 

It  tests  as  follows : 

(Test    i)     Color  in  mass Black 

(Test   4)    Fracture. Conchoidal 

(Test    5)    Lustre Bright 

(Test    6)     Streak Light  brown 

NOTE.  Extremely  thin  splinters  are  semi- 
transparent,  showing  a  deep  red  col- 
or by  transmitted  light. 

(Test   7)    Specific  gravity  at  77°  F 1.05-1,07 

(Test    90)  Hardness,  Moh's  scale Between  2  and  3 

(Test   9^)  Hardness  at  77°  F.  (penetrometer) o 

(Test    9<r)  Hardness  at  77°  F.  (consistometer) Over  150 

On  heating  in  flame Softens  and  burns  quietly 

(Test  15)     Fusing-point Does  not  fuse  without  de- 
composition 

(Test  16)    Volatile  at  325°  F.,  in  5  hrs i-  3  per  cent 

(Test  19)     Fixed  carbon 5-25  per  cent 

(Test  21 )     Soluble  in  carbon  disulfide 5-10  per  cent 

Non-mineral  matter  insoluble 85-95  per  cent 

Mineral  matter 0.2-2,5  per  cent 

(Test  22)     Carbenes o.o-i .  5  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha 0-2  per  cent 

(Test  26)     Carbon 79. 5-80.0  per  cent 

(Test  27)    Hydrogen 10. 5-12. 5  per  cent 

(Test  28)    Sulfur 4.0-6.0  per  cent 

(Test  29)    Nitrogen 1 . 8-2. 2  per  cent 

ALBERTITE 

Albertite  is  a  generic  term  applied  to  a  group  of  asphaltic  pyro- 
bitumens similar  to  the  type-substance  which  was  formerly  mined 
in  Albert  County,  New  Brunswick,  Canada.  The  name  "carboids" 
has  also  been  suggested  for  this  group  of  substances,11  and  the  terms 
"kerotenes"  and  "kerites"  to  designate  broadly  those  hydrocarbons 
that  are  insoluble  in  carbon  disulfide.  Albertites  are  characterized 
by  their 

}   Infusibility; 
2 ;   Insolubility  in  carbon  disulfide,  etc. ; 

3)  Specific  gravity  (1.07  to  i.io  at  77°  F.) ; 

4)  Percentage  of  fixed  carbon  (25  to  50  per  cent) ; 

5)  Small  percentage  of  oxygen  present  in  the  non-numeral 
constituents  (less  than  3  per  cent). 

It  occurs  in  several  localities,  of  which  the  typical  deposit  will 
be  described  first. 


XI  ALBERTITE  267 

CANADA 
Province  of  New  Brunswick. 

Albert  County.  In  1849  *  local  geologist,  Dr.  Abraham  Ges- 
ner,  discovered  a  substance  originally  termed  "albert  coal,"  subse- 
quently renamed  "albertite,"  12  on  Frederick  Brook,  a  branch  of 
Weldon  Creek,  near  Albert  Mines,  20  miles  south  of  Moncton. 
Shortly  after  this,  litigation  gave  rise  to  a  discussion  whether  or 
not  the  mineral  was  a  true  coal.  The  courts  decided  that  it  was, 
and  not  until  many  years  later  was  its  true  status  determined. 

The  principal  vein  has  been  traced  approximately  2800  ft.  and 
varies  in  thickness  from  several  inches  to  a  maximum  of  17  ft.  It  is 
connected  with  a  number  of  smaller  lateral  veins  which  in  turn  break 
up  into  still  smaller  offshoots.  The  maximum  depth  reached  by 
mining  operations  was  approximately  1400  ft,  and  it  is  estimated 
that  altogether  230,000  tons  have  been  mined.  The  main  use  of 
the  product  was  to  enrich  bituminous  coal  in  the  manufacture  of 
illuminating  gas,  but  it  is  no  longer  available,  as  the  mine  has  been 
inactive  for  many  years. 

This  occurrence  takes  the  form  of  a  true  fissure  vein  cutting 
across  a  series  of  beds  of  so-called  uoil  shales,"  which  will  be  de- 
scribed in  greater  detail  later.  Mention  should  be  made  here  that 
the  surrounding  shales  abound  in  fossil  remains  of  fish,  which  indi- 
cate that  albertite  and  its  associated  shales  are  of  animal  origin. 

On  analysis  it  tests  as  follows: 

(Test    i)    Color  in  mass Black 

(Test    2)    Homogeneity Uniform 

(Test   4)    Fracture Conchoidal  to  hackly 

(Test    5)    Lustre Bright 

(Test   6)    Streak Brown  to  black 

(Test   7)    Specific  gravity  at  77°  F 1.075-1.091 

(Test    90)  Hardness,  Moh's  scale 2 

(Test   9^)  Hardness,  penetrometer,  77°  F o 

(Test    gc)  Hardness,  consistometer,  77°  F Greater  than  150 

On  heating  in  flame Intumesces 

(Test  15)    Fusing-point Infusible.    Decomposes 

before  it  melts 

(Test  19)    Fixed  carbon 25  -50  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 2  -10  per  cent 

Non-mineral  matter  insoluble 85  -98  per  cent 

Mineral  matter o.  1-0.2  per  cent 

(Test  23)    Soluble  in  88°  petroleum  naphtha o.  5-2,0  per  cent 

(Test  24)    Solubility  in  pyridine  (boiling) 25-35  per  cent 


268 


ASPHALTIC  PYROBITVMENS 


XI 


(Test  26) 

Carbon  

/ 
Per 
Cent 

8^.44. 

II 

Per 
Cent 

8<   4.O 

/// 

Per 
Cent 
8c  <t 

/^ 

P<r 
Cent 

86  31 

r 

Per 

Cent 

87  2C 

(Test  27) 

Hydrogen.  .......... 

10  08 

92o 

°  j  •  jj 
11  20 

8  96 

96*1 

(Test  28) 

Sulfur  

o.  ±± 

.  *w 

Trace 

i  20 

Trace 

.  u,* 

(Test  29) 

Nitrogen  

l.IO 

O   42 

2   GO 

I    7C 

(Test  30) 

Oxygen  

j.  AW 

2.22 

^  •*!"*• 

•*•  7W 
I    O7 

*  •  /  J 

Undetermined  

6  .  o  A. 

O   12 

O   IO 

I    21 

IOQ.OO  100.04  IO°-35  100.24    99.83 

Province  of  Nova  Scotia. 

Pictou  County.  An  unusual  deposit  occurs  immediately  below 
the  well-known  McGregor  seam  at  Stellarton.  The  approximate 
thickness  of  the  bed  is  given  as  5  ft,  subdivided  as  follows: 

j  I }  A  layer  of  coal  I  ft.  4  in,  wide. 
2)  A  layer  of  albertite  i  ft  10  in,  wide. 
(3)  A  layer  of  pyrobituminous  shale  i  ft  10  in.  wide. 

This  species  of  albertite  has  been  exploited  under  the  name 
"stellarite."  It  seems  to  represent  a  state  of  transition  between 
true  albertite  and  the  cannel  coals,  of  which  the  Scotch  mineral 
torbanite  is  a  representative.  The  bed  contains  fossil  animal  and 
vegetable  remains.  A  splinter  of  stellarite  may  be  easily  lighted 
with  a  match  and  will  burn  with  a  bright,  smoky  flame,  throwing  off 
sparks  like  stars  (whence  its  name) .  It  was  formerly  used  to  enrich 
bituminous  coal  in  the  manufacture  of  illuminating  gas.  The  layer 
of  coal  is  an  ordinary  fat-coking  coal,  showing  a  laminated  struc- 
ture, and  containing  62.09  Per  ce^t  of  fixed  carbon  and  4.33  per 
cent  of  ash. 

The  stellarite  and  associated  pyrobituminous  shale  tests  as 
follows : 


Stellarite 
(Albertite) 

(Test    i)  Color  in  mass Brown  to  black 

(Test   4)  Fracture Hackly 

(Test    5)  Lustre Semi-bright  to  dull 

(Test   6)  Streak Reddish  brown 

(Test  7)  Specific  gravity  at  77°  F, .  1.07-1.10 

(Test  15)  Fusing-point Infusible 

(Test  19)  Fixed  carbon. 22.35-25. 23  per  cent 

(Test  ai)  Soluble  in  carbon  disulfide    2,0  per  cent 

•*  Mineral  matter 8 . 2-8 . 9  per  cent 

(Test  aj)  Moisture.. 0.2-0.3  per  cent 

(Test  26)  Carbon 88.1  per  cent 

(Test  27)  Hydrogen, n .  i  per  cent 

(Test  28)  Sulfur o.  i  per  Cent 

(Test  29)  Nitrogen 0.2  per  cent 

(Test  30)  Oxygen o.j  per  cent 


Pyrobituminou* 
Shale 

Gray  black 
Conchoidal 
Dull 
Brown 
1,56-1.78 
Infusible 

8.3-12.3  percent 
Trace 

52,0  -62.0  per  cent 
0.6  -  i.oper  cent 


0.25-  0.74  per  cent 


XI  ALBERTITE  269 

The  presence  of  the  very  small  percentage  of  oxygen  (0.5  per 
cent)  differentiates  the  material  from  lignite  and  the  other  non- 
asphaltic  pyrobitumens,  thus  corresponding  with  the  ultimate  analy- 
sis of  the  New  Brunswick  albertite. 

UNITED  STATES 
Utah. 

Uinta  County.  A  vein  of  albertite  (christened  "nigrite"  by 
Eldridge),  120  ft  long,  showing  a  maximum  width  of  20  in.,  is 
found  8  miles  from  Helper,  and  5  miles  east  of  Soldier  Summit, 
having  the  following  characteristics  : 

(Test    4)     Fracture Conchoidal 

(Test    5)    Lustre Semi-dull 

(Test    6)    Streak Brownish  black  to  black 

(Test    7)     Specific  gravity  at  77°  F 1.091-1.099 

(Test    90)  Hardness,  Moh's  scale 2 

Behavior  on  heating  in  flame Splits  and  burns 

(Test  15)    Fusingrpoint Infusible 

(Test  19)    Fixed  carbon 37~4Q  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 3-  6  per  cent 

Non-mineral  matter  insoluble 94-  2~"97-  °  Per  cent 

Mineral  matter o.  2  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha Trace 

(Test  28)    Sulfur i  .o  per  cent 

SOUTH  AMERICA 
Falkland  Islands. 

An  asphaltite  resembling  albertite,  having  a  specific  gravity  at 
77°  F.  of  1.04,  containing  3.7  per  cent  of  siliceous  ash,  and  mostly 
insoluble  in  the  usual  solvents,  has  been  reported.18 

GERMANY 

Province  of  Hanover.  A  small  deposit  of  albertite-like  pyro- 
bitumen  was  discovered  in  1870  south  of  the  village  of  Bentheim, 
east  of  the  city  of  Giidehaus.  The  material  was  mined  years  ago 
and  utilized  as  fuel,  under  the  name  "Gagat-kohle."  It  occurs  in  a 
fault  of  a  deposit  of  clayey  schist,  in  a  vein  0.50  to  0.65  m.  wide. 
The  material  has  a  high  lustre,  a  conchoidal  fracture,  a  black  streak, 
specific  gravity  at  77°  F.  1.075,  hardness  2.5,  soluble  in  carbon 
disulfide  23.5  per  cent,  slightly  soluble  ip  turpentine,  ash  0.53  per 
cent.  It  softens  and  swells  in  a  flame  and  distills  without  fusing. 
The  mine  is  now  idle,14 


270  ASPHALT1C  PYRQB1TUMENS  XI 


AUSTRALIA 

Tasmania.  A  species  of  albertite  described  under  the  name  of 
"tasmanite"  16  has  been  reported  near  the  River  Mersey  in  the 
northern  portion  of  Tasmania.  It  is  found  disseminated  in  £  pyro- 
bituminous  shale  and  complies  with  the  following  tests : 

(Test    l)    Color  in  mass Black 

(Test    2)    Homogeneity Uniform 

(Test   4)    Fracture Conchoidal 

(Test    5)    Lustre Bright 

(Test   6)    Streak Yellowish  brown 

(Test   7)    Specific  gravity  at  77°  F i .  10 

(Test   go)  Hardness,  Moh's  scale 2 

(Test  15)    Fusing-point Infusible 

(Test  21)     Soluble  in  carbon  disuifide Trace 

Mineral  matter 8-14  per  cent 

(Test  26)    Carbon 79-^  "79-3  per  cent 

(Test  27)    Hydrogen 7.2  -  7.4  per  cent 

(Test  28)     Sulfur 5.28-  5.32  per  cent 

(Tests  29  and  30)    Nitrogen  and  oxygen 4. 93  per  cent 

PORTUGUESE  WEST  AFRICA 

Province  of  Angola. 

District  of  Libollo.  A  species  of  albertite  is  reported  at  Calu- 
cala,  14  miles  north  of  the  railway  station  Zenza  .do  Itombe  (which 
is  1 8  miles  east  of  Luanda  on  the  Luanda-Malange  Railway  line) 
under  the  name  "libollite."  16 


IMPSONITE 

This  represents  the  final  stage  in  the  metamorphosis  of  asphal- 
tites  and  asphaltic  pyrobitumens.    It  is  characterized  by  its : 

1 i )  Infusibility  and  insolubility  in  carbon  disuifide ; 

(2)  Specific  gravity  (i.io  to  1.25) ; 

(3)  High  percentage  of  fixed  carbon  (50  to  85  per  cent) ; 

(4)  Comparatively  small  percentage  of  oxygen  (less  than  5  per 
cent)t  which  differentiates  it  from  the  non-asphaltic  pyrobitumens. 

The  weathered  asphaltites  taken  from  the  exposed  portions  of 
the  vein,  where  they  have  been  subjected  for  centuries  to  the  action 


XI  IMPSONITE  271 

of  the  elements,  closely  resemble  impsonite  in  their  physical  and 
chemical  properties,  and  may  therefore  be  classified  as  such.    Out- 
crops of  grahamite  are  especially  prone  to  metamorphize  into  imp- 
sonite, and  many  prospectors  have  been  misled  on  this  account 
The  following  represent  the  most  important  deposits : 


,  IT 


NORTH  AMERICA 

UNITED  STATES 
Oklahoma. 

La  Flore  County.  One  of  the  largest  deposits  of  impsonite  oc- 
curs 2  miles  east  of  Page  on  the  southern  slope  of  Black  Fork 
Mountain  (S  J4,  Sec  24,  T  3  N,  R  26  E),  filling  a  fissure  caused 
by  a  fault.  The  vein  is  about  10  ft  thick,  and  has  been  mined  to 
some  depth.  It  complies  with  the  following  tests: 

(Test    i)     Color  in  mass Black 

(Test   4)    Fracture Hackly 

(Test    5)    Lustre Semi-dull 

(Test    6)    Streak Black 

(Test    7)    Specific  gravity  at  77°  F i .  235 

(Test    9*)  Hardness,  Moh's  scale 2-3 

Heating  in  flame Decrepitates 

(Test  15)    Fusing-point Infusible 

(Test  19)    Fixed  carbon 75.0-81 .6  per  cent 

(Test  21)    Soluble  in  carbon  disulfide 4-  6  per  cent 

Non-mineral  matter  insoluble 93-96  per  cent 

Mineral  matter o .  7-2 , 5  per  cent 

(Test  24)    Solubility  in  pyridine  (boiling) 3. 88  per  cent 

(Test  25)    Moisture o.  i-i .  5  per  cent 

(Test  28)    Sulfur i  ,69  per  cent 

Murray  County.  Impsonite  has  been  reported  5  miles  north- 
east of  Dougherty  (Sec.  33,  T  i  S,  R  3  E),  in  a  vein  about  18  in. 
thick  at  the  top  and  7  ft.  at  the  bottom.  Its  characteristics  are 
similar  to  the  preceding. 

Arkansas. 

Scott  County.  Another  deposit  of  impsonite,  referred  to  as 
"arkosite,"  18  occurs  in  the  western  part  of  Fourche  Mountain, 
about  1 2  miles  east  of  the  Black  Fork  Mountain  locality  in  Okla- 
homa. The  exact  locality  is  I  mile  east  of  Eagle  Gap,  and  2  miles 


272  ASPHALT1C  PYROBITVMENS  XI 

££st  of  Harris,    It  occurs  in  a  region  of  shale  and  sandstone,  and 
tests  as  follows: 

;        (Test    i>    Color  in  mass Black 

(Test  4)    Fracture Hackly 

(Test    5)    Lustre Semi-dull 

(Test  6)    Stfeak Black 

(Test  7)    Specific  gravity  at  77°  F i  .25 

(Test   94)  Hardness,  Moh's  scale 3 

Heating  in  flame Decrepitates 

(Test  15)    Fusing-point Infusible 

(Test  19)    Fixed  carbon 80,  o  per  cent 

(Test  ai)    Soluble  in  carbon  disulfide Trace 

Non-mineral  matter  insoluble 99. 3  per  cent 

Mineral  matter 0.6  per  cent 

(Test  28)    Sulfur 1.38  per  cent 

Nevada. 

Eureka  County.  A  deposit  is  reported  15  miles  south  of  Pali- 
sade in  Pine  Creek  valley,  in  a  vein  filling  a  fault  about  300  ft.  long 
and  of  unknown  depth.  Its  physical  and  chemical  characteristics 
are  similar  to  the  preceding.1 


,  19 


Michigan. 

Keweenaw  County.  An  interesting  formation  has  been  de- 
scribed in  the  vicinity  of  the  Porcupine  Mountains  in  the  southwest 
part  of  Keweenaw  Point,  in  which  the  impsonite  acts  as  a  cement  in 
sandstone  beds  carrying  grains  of  native  copper.  Much  of  the  imp- 
sonite is  surrounded  by  copper,  giving  rise  to  the  assumption  that 
the  former  was  present  prior  to  the  deposition  of  the  copper.  The 
impsonite  analyzes:  64.8  per  cent  fixed  carbon  and  33.3  per  cent 
ash  containing  2  per  cent  copper.2 


,  20 


SOUTH  AMERICA 
PERU  21 


Canta  (Department  of  Lima)  and  Yauli  (Depart- 
ment of  Junin).  More  than  a  do^en  veins  have  been  found  in  the 
District  of  Yantac,  about  28  miles  from  CasapiUica,  on  the  Central 
Railway  of  Peru,  near  the  city  o}f  Marcapomacocha  (see  Fig.  87), 
also  at  Cajatambo  (Cojcitambo),  having  a  specific  gravity  qf  1.25,  a 


XI  IMPSONIT&  273 

bright  conchoidal  fracture,  a  black  streak  and  1,6  per  cent  ash,82 
They  occur  along  both  slopes  of  the  western  Cordillera  of  the 
Andes,  at  altitudes  of  12,000  to  16,000  ft,  and  vary  in  thickness 
from  a  few  inches  to  5  ft.  The  average  composition  shows :  mois- 
ture 5.2  per  cent,  fixed  carbon  72.2  per  cent,  volatile  10.3  per  cent, 
and  ash  12.3  per  cent  (containing  5  to  16  per  cent  of  vanadic  oxides 
V2O5).  The  presence  of  tiny  fissures  radiating  from  the  main  vein, 
and  the  inclusion  of  "horses"  in  the  vein  proper  differentiate  the 
material  from  a  coal  formation.  It  is,  however,  distinctly  anthra- 
cite in  character,  burning  with  little  to  no  flame. 

Llacsacocha  Mine  occurs  13  miles  by  trail  south  of  the  town  of 
Yauli,  extending  for  more  than  1200  ft.  in  limestone  formation, 
having  numerous  lenses  and  faults.  It  is  black  and  lustrous,  free 
from  pyrites,  and  contains:  fixed  carbon  88.2  per  cent,  volatile  9.0 
per  cent,  and  ash  2.8  per  cent  (carrying  15  per  cent  vanadic  oxide). 

Rumichaca  Mine  at  Minasragra,  near  Cerro  de  Pasco,  yields 
about  80  per  cent  of  the  world's  supply  of  vanadium  and  is  the 
largest  of  all  in  the  Yauli  district.  Being  close  to  the  railroad,  it 
has  been  largely  worked  during  the  past  ten  years,  and  used  as  a 
fuel.  The  vein  carries  from  a  few  inches  to  40  ft  in  width  and 
contains  an  average  of  16  per  cent  ash  (carrying  5.3  per  cent  vana- 
dic oxide) — otherwise  it  is  similar  in  composition  to  the  foregoing. 

Negrita  Mine  is  situated  15  miles  from  the  railroad,  near  Hulla- 
cocha  Lake,  occurring  as  a  true  fissure  vein,  cutting  across  limestone 
and  shale.  Three  lenses  yielded  2000  tons.  An  average  analysis 
showed  9.5  per  cent  ash  (carrying  5  per  cent  vanadic  oxide). 

Cacharata  Mine  is  located  about  1000  yd.  from  the  previous 
vein  and  measures  2  ft.  wide,  being  similar  in  composition. 

Province  of  Huarochiri  (Department  of  Lima).  Narrow  and 
irregular  veins  occur  at  Sillapata,  15  miles  from  the  railway  station 
of  Matucana,  running  high  in  ash  (averaging  slightly  less  than  i  per 
cent  of  vanadic  oxide). 

BRAZIL 

State  of  Sao  Paulo.  Irnpsonite  has  been  found  in  a  dyke  near 
Limeira,  analyzing:  fixed  carbon  76  per  cent,  volatile  matter  5  per 
cent,  and  ash  1 6  per  cent/ 


.83 


274  ASPHALTIC  PYROB1TVMENS  XI 

AUSTRALIA 

West  Australia.  A  deposit  of  impsonite  has  been  reported  in 
West  Australia  having  a  specific  gravity  of  1.154,  moisture  0.37 
per  cent,  fixed  carbon  56.27  per  cent,  volatiles  41.91  per  cent,  and 
ash  1.82.  It  does  not  melt  up  to  300°  C*4 


CHAPTER  XII 
PYROBITUMINOUS  SHALES1 

Under  this  heading  will  be  considered  the  oil-forming  shales 
containing  pyrobitumens  associated  with  earthy  matter,  which  will 
produce  oily  or  tarry  distillates  upon  being  subjected  to  destructive 
distillation.  Oil-bearing  and  asphalt-bearing  shales  from  which  pe- 
troleum or  asphalts  may  be  extracted  writh  solvents  are  not  included. 
The  well-known  shales  in  France  occurring  at  Autun  (Saone-et- 
Loire)  and  Bruxieres-les-Mines  (Allier)  consisting  of  semi-liquid 
asphalt  associated  with  shales  shall  accordingly  be  excluded,  al- 
though these  have  been  classified  indiscriminately  with  the  true  pyro- 
bituminous  shales  by  other  writers. 

Pyrobituminous  shales  may  be  sub-divided  into  two  classes : 

1 i )  Asphaltic  pyrobituminous  shales  in  which  asphaltic  pyro- 
bitumens (elaterite,  wTurtzilite,  albertite  or  impsonite)  are  associated 
with  shales. 

(2 )  Non-asphaltic  pyrobituminous  shales  in  which  non-asphaltic 
pyrobitumens  (cannel  coal,  lignite  or  bituminous  coal)  are  associated 
with  shales. 

Little  or  no  attempt  has  been  made  to  differentiate  between 
these  two  groups,  on  account  of  the  difficulty  in  identifying  the 
bituminous  material  present.  This  will  become  apparent  when  it  is 
considered  that  pyrobitumens  are  more  or  less  insoluble  in  solvents 
and  are  moreover  masked  by  the  associated  mineral  matter,  which 
interferes  with  the  usual  distinguishing  tests,  such  as  the  specific 
gravity,  lustre,  streak,  etc.  Up  to  the  present  time  all  pyrobitu- 
minous shales  have  been  referred  to  under  the  general  term  "oil 
shales,"  which  is  really  a  misnomer. 

The  following  means  are  suggested  to  differentiate  the  two 
classes: 

( i )   By  the  pyrobitumens  found  locally. 

The  presence  of  asphaltic  bitumens  in  the  vicinity  would  indicate 
an  asphaltic  pyrobituminous  shale.  Similarly,  non-asphaltic  pyro- 

275 


276 


PYROBITUMINOUS  SHALES 


XII 


bitumens  would  tend  to  establish  the  identity  of  the  shale  as  non- 
asphaltic.    If  both  types  are  present,  the  eviaence  is  non-conclusive. 


(2)   By  the  associated  fossil  remains. 


If  vegetable  (plant)  fossil  remains  only  are  found  associated 
with  the  shale,  the  indications  are  that  it  is  non-asphaltic,  since  it 
is  definitely  established  that  the  non-asphaltic  pyrobitumens  are  of 
vegetable  origin.  On  the  other  hand,  if  animal  (fish  or  mollusc) 
fossil  remains  are  present,  the  shale  will  more, than  likely  represent 
the  Asphaltic  pyrobituminous  variety, 

(i)   Effect  of  heat  on  the  solubility. 

On  heating  in  a  closed  retort  to  300°  to  400°  C,  asphaltic  pyro- 
bituminous shales  will  depolymerize  and  become  more  soluble  in 
carbon  disulfide,  whereas  the  non-asphaltic  pyrobituminous  shales 
remain  unaffected.  It  is  also  interesting  to  note  that  the  bituminous 
constituents  of  non-asphaltic  pyrobituminous  shales  are  rendered 
fusible  and  soluble  by  neating  the  finely  powdered  shale  to  500  to 
600°  F.  in  a  closed  retort  with  a  residual  oil  derived  from  petro- 
leum, or  with  coal  tar.8 

(4)  By  the  percentages  of  fixed  carbon  and  oxygen  (calculated 
on  the  basis  of  the  non-mineral  matter  present).  These  two  cri- 
teria, considered  together,  furnish  the  most  reliable  means  of  dis- 
tinguishing between  the  two  classes  of  shale,  as  will  be  observed 
from  the  following  figures,  calculated  on  the  basis  of  the  non-min- 
eral constituents  present : 


Fixed  Carbon 
(Calculated  on  the 
Ash-free  Basis) 
Per  Cent 

Oxygen  (Calculated 
on  the  Ash-free  Basis) 
Per  Cent 

Asphaltic  Pyrobituminous  Shaks; 
Wurtzilite  shalefc  

i—  IO 

Less  than  2. 

Albert!  te  shales.  ,  

c—  <5i? 

Non*asphaUie  Pyrobituminous  Shaks: 
Cannel  coal  shales  

5^*5 

£—  •  'irt 

Less  than  3 

Lignite  shales  

5   -*0 

1  C  —  1ft 

5-10 

¥  **-  -  •**  Q 

Bituminous  coal  shales  

*J  Ju 

iC—CO 

15    25 

ff     T  O 

xj  y-> 

3*s 

It  will  be  noted  that  the  percentage  of  fixed  carbon  calculated  on 
the  mineral-free  basis,  runs  Ipwer  than  in  the  corresponding  (pure) 
pyrobitumens,  due  to  the  presence  of  the  mineral  matter,  which 
assists  in  the  combustion  of  the  xarbon  during  the  test,  decreasing 
the  yield  of  "fixed  carbon,"  and  at  the  same  time  increasing  the 
percentage  of  volatile  constituents.  This  is  important  from  *  com- 


XII  PYROBITUMINOUS  SHALES  277 

mercial  viewpoint  The  most  valuable  pyrobituminous  shales  are 
those  which  produce  the  largest  amount  of  volatile  matter  when 
subjected  to  destructive  distillation.  This  is  true  with  the  albertitic, 
cannel  coal  (torbanitic)  and  lignitic  shales,  whereas  the  bituminous 
coal  shales  yield  but  little  volatile  matter  and  have  no  commercial 
importance. 

Two  types  of  bituminous  constituents  are  present  in  non- 
asphaltic  pyrobituminous  shales,  viz.:  (i)  macerated  and  carbon- 
ized plant  remains  similar  to  coal,  and  (2)  yellow  resinous  bodies 
representing  the  last  stage  in  the  oxidation  of  the  woody  tissue, 
Elaterite,  wurtzilite  and  impsonite  shales  are  rarely  found. 

Pyrobituminous  shales  generally  contain  more  than  33  per  cent 
of  associated  mineral  constituents.  The  non-mineral  constituents 
present  in  non-asphaltic  pyrobituminous  shales  have  been  designated 
by  the  terms  "kerogen"  s  or  "petrologen."  * 

From  the  foregoing  it  will  be  apparent  that  the  subject  of  "pyro- 
bituminous shales"  is  an  extremely  complicated  one,  still  requiring 
a  vast  amount  of  research  work  before  all  the  deposits  can  be  cor- 
rectly classified. 

Pyrobituminous  shales  are  treated  exclusively  by  subjecting 
them  to  a  process  of  destructive  distillation  in  suitable  retorts  to 
recover  the  tarry  distillate  and  ammonium  sulfate  as  will  be  de- 
scribed in  Chapter  XVI.  The  intrinsic  value  of  the  shale  is  de- 
pendent upon  the  amount  of  shale  tar  and  ammonium  sulfate 
obtained. 

A  detailed  description  of  the  individual  deposits  of  pyrobitumi- 
nous shales  does  not  fall  within  the  scope  of  this  publication. 


PART  III 
TARS,  PITCHES,  AND  PYROGENOUS  ASPHALTS 


CHAPTER  XIII 
GENERAL  METHODS  OF  PRODUCING  TARS 

Tars  constitute  the  volatile  oily  decomposition  products  ob- 
tained in  the  pyrogenous  treatment  of  bituminous  and  other  organic 
substances.  The  pyrogenous  treatment  embraces  three  processes, 
viz. : 

1 i )  Subjecting  to  heat  alone  without  access  of  air,  often  termed 
"destructive  distillation,"  and  sometimes  referred  to  as  "pyrolysis." 

(2)  Partial  combustion,  which  may  take  place  either  in  an  at- 
mosphere of  air  and  steam  (in  gas  producers)  or  with  a  limited 
access  of  air. 

(3)  Cracking  oil  vapors  at  high  temperatures. 

Practically  all  organic  substances  which  undergo  decomposition 
produce  tars  upon  being  subjected  to  heat,  provided  they  yield  a 
substantial  proportion  of  volatile  decomposition  products,  the  tem- 
perature is  sufficiently  high  to  bring  about  the  decomposition,  and 
air  is  entirely  or  partially  excluded  during  the  pyrogenous  treat- 
ment If  the  organic  substance  does  not  contain  volatile  matter,  as 
proves  the  case  with  anthracite  coal  or  graphite,  no  tar  will  result. 
If  air  is  present  in  too  large  a  quantity,  the  products  of  decomposi- 
tion will  undergo  complete  combustion,  and  the  tar  will  be  con- 
sumed. Materials  which  evaporate  (i.  e.}  distil  undecomposed),  or 
sublime,  will  remain  unchanged  in  composition,  and  products  which 
explode  are  converted  into  permanent  gases,  without  the  formation 
of  tars. 

At  the  present  time  tars  are  produced  commercially  from  the 
following  products : 

278 


XIII 


GENERAL  METHODS  OF  PRODUCING  TARS 


279 


(1)  Bituminous  substances  including  peat,  lignite,  bituminous 
coal,  petroleum  and  pyrobituminous  shales. 

(2)  Certain   other   organic    substances   including   wood,    and 
bones. 

The  following  will  give  a  synoptical  outline  of  the  raw  materials 
used,  the  modes  of  treatment  and  the  kinds  of  tar  produced: 


Raw  Materials  Used 

Heat  Alone 
("  Destructive 
Distillation") 

Partial  Combustion 

"Cracking" 

Air  and  Steam 
("Producers") 

Limited  Access 
of  Air 

Bituminous  substances: 
Petroleum  products.  .  .  . 
Peat  

Wax  tailings 

Peat  tar 
Lignite  tar 
Shale  tar 
Gas-works  coal 
tar 
Coke-oven  coal 
tar 

Wood  tar 
Bone  tar  

[Pressure  tar 
I  Oil-gas  tar 
I  Water-gas  tar 

Peat  tar 

Lignite  tar 
Shale  tar 

Producer-gas 
coal  tar 

Lignite  

Pyrobituminous  shales. 
Bituminous  coals  

Other  Organic  Materials: 
Wood  

Blast  furnace 
coal  tar 

Bones  

Petroleum  products  (e.g.,  "gas  oils")  upon  being  subjected  to  a 
high  temperature  under  more  or  less  pressure  in  a  closed  retort  will 
result  in  the  formation  of  oil-gas  tar;  and  when  sprayed  on  incan- 
descent anthracite  coal  or  coke  result  in  the  production  of  water-gas 
tar.  Peat,  lignite  and  pyrobituminous  shales  result  in  the  formation 
of  peat-,  lignite-  and  shale-tars  respectively:  (i)  when  subjected  to 
destructive  distillation,  or  (2)  upon  undergoing  partial  combustion 
in  an  atmosphere  of  air  and  steam  in  a  so-called  "gas  producer." 
Tars  resulting  from  these  two  processes  are  similar  in  composition 
and  hence  are  designated  by  the  same  name.  Destructive  distilla- 
tion yields  a  larger  percentage  of  tar  than  partial  combustion  in  an 
atmosphere  of  air  and  steam. 

Bituminous  coals  form  different  kinds  of  tar,  depending  upon 
the  nature  of  the  process.  Thus  gas-works  coal  tar  and  coke-oven 
coal  tar  are  produced  by  the  destructive  distillation  of  bituminous 
coal  in  gas-works  retorts  and  coke-ovens  respectively.  Producer-gas 


280  GENERAL  METHODS  OF  PRODUCING  TARS  XIII 

coal  tar  is  derived  from  the  partial  combustion  of  bituminous  coal 
in  an  atmosphere  of  air  and  steam  in  a  gas  producer.  Blast-furnace 
coal  tar  results  from  the  partial  combustion  of  bituminous  coal  in  a 
limited  access  of  air  in  a  so-called  "blast  furnace,"  Destructive 
distillation  of  wood  results  in  the  formation  of  wood  tar,  and  of 
bones  in  the  production  of  bone  tar. 

In  the  order  of  their  commercial  importance,  based  on  the  quan- 
tities produced  annually,  tars  may  be  grouped  as  follows,  viz.: 
coal  tar  is  produced  in  the  largest  quantity,  water  and  oil-gas  tars 
come  next,  and  wood  tar  follows  in  sequence.  Insignificant  quan- 
tities of  producer-gas  coal  tar,  bone  tar,  blast-furnace  tar,  peat-, 
lignite-  and  shale-tars  are  produced  in  the  United  States.  Lignite 
tar  is  produced  in  comparatively  large  quantities  in  Germany.  The 
production  of  peat-  and  bone-tar  has  not  assumed  great  importance 
anywhere. 

The  following  tars  have  been  described  in  the  literature,1  pro- 
duced by  the  destructive  distillation  of  the  corresponding  substance; 
but  have  but  little  commercial  value : 

Montan-wax  tar ; 2  beeswax-tar ;  tars  derived  from  the  destruc- 
tive distillation  of  vegetable  and  animal  oils;  linoleum  tar  derived 
from  linoleum  waste;  cork  tar;  leather  tar; 3  tanning  residues;  sea- 
weed tar;  sulfite  cellulose  tar  (tall  oil  tar)  produced  from  the  de- 
structive distillation  of  sulfite  cellulose  liquor;4  lignin  tar;  amber 
tar,  also  tars  derived  from  other  fossil  resins;  straw  tar;  tars  de- 
rived from  seed  husks  and  hulls; 5  tobacco  tar;  bagasse  tar; 6  mo- 
lasses tar;7  tar  from  beet  residues  in  sugar  manufacture;  tar  from 
potato  residues  resulting  from  fermentation;8  tars  from  fermenta- 
tion residues  of  various  sorts;  yinasse  tar;  anthracene-oil  tar  ob- 
tained as  residue  in  anthracene  oil  distillation;  fusel-oil  tar  obtained 
on  distillation  of  fusel  oil ;  asphalt  tar  obtained  on  destructive  distil- 
lation of  natural  rock  asphalts  (e.g.,  at  Ragusa,  Italy;  Tyrol,  Aus- 
tria; and  at  other  localities),  etc. 

The  corresponding  pitches  are  produced  by  distilling  the  respec- 
tive tars  listed  above ;  i.e.,  montan-tar  pitch,  beeswax-tar  pitch,  vege- 
table- (or  animal)  oil-tar  pitch,  linoleum-tar  pitch,  cork-tar  pitch, 
leather-tar  pitch,  tannin-tar  pitch,  seaweed-tar  pitch,  sulfite-cellulose- 
tar  pitch  (tall-oil  pitch),  lignin-tar  pitch,  amber-tar  pitch,  straw-tar 
pitch,  seed-tar  pitch,  tobacco-tar  pitch,  bagasse-tar  pitch,  molasses- 
tar  pitch,  beet-residue-tar  pitch,  potato-residue-tar  pitch,  fermenta- 


XIII  DESTRUCTIVE  DISTILLATION  281 

tion-residue-tar  pitch,  vinasse-tar  pitch,  anthracene-oil-tar  pitch, 
fusel-oil-tar  pitch,  naphthylamine  pitch,  cumarone  pitch,  cresol  pitch 
(carbol  pitch),  asphalt-tar  pitch,  etc. 

We  will  now  consider  the  various  processes  for  producing  tars 
in  greater  detail. 

DESTRUCTIVE  DISTILLATION 

This  process  is  used  for  destructively  distilling  infusible  organic 
substances  including  non-asphaltic  pyrobitumens,  pyrobituminous 
shales,  wood  and  bones.  It  consists  in  heating  the  substance  to  a 
high  temperature  in  a  still  from  which  air  is  excluded,  and  the  dis- 
tillation is  continued  until  the  volatile  constituents  are  driven  off  and 
the  residue  carbonizes.  The  volatile  constituents  are  grouped  into 
two  classes,  viz,:  non-condensable  and  condensable  products,  the 
former  including  the  permanent  gases,  and  the  latter,  the  aqueous 
liquor  and  tar. 

The  nature  of  the  ingredients  formed  during  the  distillation  de- 
pends largely  upon  the  nature  of  raw  material  used  and  the  tem- 
perature at  which  it  undergoes  decomposition.  As  a  rule,  the  older 
the  substance  from  a  geological  standpoint,  the  higher  will  be  the 
temperature  at  which  it  decomposes.  At  low  temperatures,  we  find 
aliphatic  (straight  chain)  hydrocarbons  in  the  tar,  also  varying 
amounts  of  phenolic  bodies,  of  toluene  and  naphthalene,  but  no 
benzene  or  anthracene.  This  is  true  in  the  case  of  peat,  lignite, 
cannel  coal  and  pyrobituminous  shales.  Where  the  destructive  dis- 
tillation takes  place  at  a  high  temperature,  aromatic  hydrocarbons 
will  predominate,  including  benzene  and  anthracene.  This  is  true 
with  bituminous  coals.  The  aqueous  liquor  will  show  an  acid  reac- 
tion in  the  case  of  wood  and  peat,  and  an  alkaline  reaction  with 
lignite,  coals  and  pyrobituminous  shales. 

In  general,  the  yield  of  tar  depends  upon  five  factors,  viz. :  the 
composition  of  the  substance,  the  temperature,  the  time  of  heating, 
the  pressure,  and  upon  the  efficiency  of  the  condensing  system. 
These  will  be  considered  in  greater  detail. 

The  Composition  of  the  Substance,  (a)  The  Percentage  of 
Volatile  Constituents.  The  greater  the  percentage  of  volatile  con- 
stituents, and  conversely  the  smaller  the  percentage  of  "fixed  car- 
bon," the  larger  will  be  the  yield  of  tan  Figured  on  the  basis  of 


282 


GENERAL  METHODS  OF  PRODUCING  TARS 


XIII 


&\ja  vrjLitju  juzw*4rf  *rj.j±j.msjLsu    I/JT    i  xti/Asi/  ujxv  vj    .x /3*Y4j  ^VXAJL 

the  dry  weight  of  the  non-mineral  constituents,  the  yield  of  volatile 
matter  will  range  as  follows,  commencing  with  the  highest:  wood, 
peat,  lignite,  bituminous  coal.  The  yields  of  tar  follow  in  the  same 
sequence,  viz. : 

Wood 10  -20  per  cent 

Peat 7i~i5  per  cent 

Lignite 5  -10  per  cent 

Bituminous  coal , 3  -  7  per  cent 

(b)  The  Percentage  of  Oxygen  in  the  Fuel.  As  a  general  rule, 
the  greater  the  percentage  of  oxygen  in  the  fuel,  the  greater  will  be 
the  yield  of  tar.  Georg  Lunge  9  cites  the  following  figures  to  show 
the  relation  between  the  percentages  of  oxygen,  tar,  and  water, 
based  on  the  dry  weight  of  fuel: 


Fuel  Contains 
Per  Cent 

Yield  Tar, 
Per  Cent 

Yield  Water, 
Per  Cent 

Oxygen    <-6i  

310 

A      <8 

Oxygen    65-7^  

4.6c 

<.86 

Oxygen    7J~9  

c.o8 

6,80 

Oxygen   9-1  1  

$.48 

8,60 

Oxygen  11-13  

r,  ro 

7  86 

The  Temperature,  (a}  The  Temperature  at  which  the  Fuel 
Decomposes.  As  stated  previously,  each  type  of  fuel  has  a  definite 
temperature  at  which  distillation  commences.  The  older  the  fuel 
from  a  geological  standpoint,  the  higher  will  be  this  temperature, 
and  hence  the  greater  will  be  the  yield  of  coke,  and  the  smaller  that 
of  tar.  It  would  appear  that  a  preliminary  decomposition  approach- 
ing a  state  of  fusion  occurs  at  this  temperature,  which  remains  fairly 
constant  until  the  carbonization  is  complete.  The  coke-forming 
property  of  bituminous  coals  depends  upon  the  presence  of  con- 
stituents melting  at  a  lower  temperature  than  that  at  which  carboni- 
zation occurs. 

(b)  The  Temperature  at  Which  the  Distillation  Is  Performed. 
This  is  distinct  from  the  preceding,  and  is  determined  by  the  quan- 
tity and  intensity  of  the  heat  applied  externally  to  the  retort  in 
which  the  destructive  distillation  takes  place.  It  depends  upon  the 
nature  of  the  heating  medium,  and  the  manner  in  which  it  is  applied. 
The  temperature  may  be  close  to  that  at  which  the  fuel  undergoes 


XIII  DESTRUCTIVE  DISTILLATION  283 

distillation,  or  it  may  be  vastly  in  excess  thereof.  The  higher  the 
temperature  above  that  necessary  to  cause  incipient  decomposition, 
the  smaller  will  be  the  yield  of  tar,  and  the  larger  that  of  gas;  more- 
over, a  high  temperature  results  in  the  formation  of  a  larger  per- 
centage of  free  carbon  in  the  tar,  due  to  greater  decomposition 
("cracking")  of  the  distillate. 

Aromatic  hydrocarbons,  upon  being  subjected  to  a  gradually  in- 
creasing temperature  (650-800°  C),  are  transformed  as  follows: 

Higher  benzene  homologues-*Lower  benzene  homologues-»Di- 
phenyl-»Naphthalene-»  Anthracene. 

At  temperatures  above  800°  C.,  the  anthracene  is  decomposed 
into  carbon  and  gas.10 

The  Time  of  Heating,  (a)  Thickness  of  the  Fuel  Layer.  The 
deeper  the  layer  of  fuel  in  the  retort  or  furnace,  the  greater  the 
super-heating,  and  consequently  the  smaller  will  be  the  yield  of  tar 
and  the  larger  that  of  gas.  When  the  layer  is  deep,  the  volatile 
portions  are  compelled  to  pass  through  a  mass  of  incandescent  fuel, 
so  that  the  temperature  of  the  gases  is  increased,  due  to  the  greater 
time  of  contact.  This  is  the  underlying  principle  in  the  manufacture 
of  generator  gas. 

It  follows  also  that  the  greater  the  area  of  contact  between  the 
fuel  and  the  heating  surface,  the  shorter  time  it  will  take  to  raise  the 
temperature  of  the  former  the  requisite  degree.  Small  charges  of 
fuel  may  thus  be  heated  more  rapidly,  which  is  conducive  to  the 
formation  of  a  greater  proportion  of  gas  and  tar  and  a  smaller  yield 
of  coke.  Slow  heating,  on  the  other  hand,  results  in  the  production 
of  a  large  proportion  of  coke,  and  smaller  proportions  of  gas  and 
tar  respectively.  It  is  for  this  reason  that  comparatively  small  and 
narrow  retorts  are  used  for  the  manufacture  of  illuminating  gas,  and 
very  much  larger  chambers  where  coal  is  treated  to  obtain  coke. 

(b)  Size  of  the  Fuel.  The  size  of  the  lumps  of  fuel  has  an  im- 
portant bearing  on  the  time  of  heating.  If  the  lumps  are  too  fine, 
they  will  pack  together  to  such  an  extent  that  insufficient  space  is  left 
between  them  for  the  transfer  of  heat  by  the  gaseous  products. 
On  the  other  hand,  if  the  lumps  are  too  large,  it  will  take  an  abnor- 
mally long  time  for  the  carbonization  process  to  reach  the  center  of 
each  lump,  since  the  heat  conduction  of  the  fuel  itself  is  poor. 


284  GENERAL  METHODS  OF  PRODUCING  TARS  XIII 

(c)  Construction  of  the  Retort  or  Furnace.  The  thickness  of 
the  walls,  the  method  of  heating,  the  size  as  well  as  the  nature  of 
the  material  of  which  the  retort  is  constructed,  all  tend  to  influence 
the  time  of  heating.  Small  units,  the  use  of  preheated  gases  for 
supporting  the  combustion,  and  thin  retort  walls  constructed  of  ma- 
terials which  have  a  relatively  high  conductivity  at  elevated  tem- 
peratures, serve  to  decrease  the  time  of  heating. 

The  Pressure.  The  greater  the  pressure,  the  longer  are  the 
volatile  products  forced  to  remain  in  contact  with  the  hot  retort  and 
incandescent  fuel,  and  the  greater,  therefore,  will  be  the  carboniza- 
tion. The  use  of  reduced  pressure  hastens  the  removal  of  the  vola- 
tile constituents  and  serves  to  increase  the  outputs  of  gas  and  tar, 
and  reduce  the  yield  of  coke*  At  the  same  time,  the  period  of  dis- 
tillation is  increased.  In  manufacturing  illuminating  or  fuel  gas, 
modern  practice  consists  in  carrying  out  the  distillation  under  a 
moderate  vacuum.  On  the  other  hand,  when  the  main  object  is  to 
produce  coke,  the  pressure  of  the  gas  inside  the  retort  is  purposely 
allowed  to  increase  somewhat. 

The  Efficiency  of  the  Condensing  System.  As  the  vapors  leave 
the  retort,  oven,  blast-furnace,  or  producer  at  500  to  800°  CM  all 
the  constituents  exist  in  the  gaseous  state,  excepting  the  "free  car- 
bon" derived  from  the  decomposition  of  the  gases  in  contact  with 
the  highly  heated  walls,  and  the  particles  of  mineral  matter  which 
are  carried  over  mechanically.  The  vapors  are  composed  of  a  mix- 
ture of  substances,  .some  congealing  to  solids,  others  condensing  to 
liquids,  and  still  others  remaining  as  permanent  gases  at  atmos- 
pheric temperature  and  pressure.  As  the  vapors  cool,  the  solids  and 
liquids  separate  out,  forming  the  tar.  This  separation  is  progressive, 
the  higher  boiling-point  constituents  condensing  first,  followed  by 
substances  of  lower  boiling-points,  and  finally  liquids  boiling  slightly 
above  atmospheric  temperature.  With  this  in  view,  the  vapors  may 
either  be  cooled  slowly,  or  they  may  be  cooled  rapidly,  so  that  all 
condensable  constituents  are  caught  together  in  the  form  of  "tar," 
to  be  redistilled  later  into  its  components.  It  is  a  singular  fact,  that 
even  when  the  vapors  have  been  thoroughly  cooled,  the  tar  will  not 
separate  out  completely,  without  further  treatment.  Part  remains 
suspended  in  the  gases  as  infinitesimally  fine  globules,  known  as  a 
"tar  fog."  This  term  is  most  expressive,  since  its  behavior  is  very 


XIII  PARTIAL  COMBUSTION  WITH  AIR  AND  STEAM  285 

similar  to  that  of  an  ordinary  fog,  alluding  to  the  weather.  Mere 
cooling  will  not  condense  a  "tar  fog,"  accordingly  other  means  must 
be  employed. 

PARTIAL  COMBUSTION  WITH  AIR  AND  STEAM 

This  takes  place  in  manufacturing  producer  gas.  Several  forms; 
of  producers  are  in  use,  and  peat,  lignite,  pyrobituminous  shale,  or 
bituminous  coal  are  variously  employed  as  fuel.  The  reaction  which 
ensues  may  be  expressed  as  follows,  in  which  "C"  represents  the 
carbonaceous  matter  present  in  the  form  of  fuel: 


The  resulting  gas,  known  as  "producer  gas,"  is  composed  of  carbon 
monoxide  with  a  smaller  proportion  of  hydrogen.  When  anthracite 
coal  or  coke  is  used  as  fuel,  no  tar  results  ;  with  bituminous  coal,  tar 
is  formed  in  certain  types  of  producers  but  not  in  others;  and  with 
peat  or  lignite,  tar  is  produced  in  all  types,  on  account  of  the  readi- 
ness with  which  they  volatilize  at  low  temperatures,  and  the  com- 
paratively large  proportion  of  volatile  constituents  present  These 
tars  correspond  very  closely  in  physical  and  chemical  properties  to 
the  ones  obtained  from  the  corresponding  processes  of  destructive 
distillation,  but  with  the  former  the  yield  is  smaller,  since  most  of 
the  tarry  matter  is  consumed. 

Lignite  carrying  a  moderate  proportion  of  mineral  matter  (e.g., 
Messel  lignite)  is  treated  in  a  special  form  of  producer  to  obtain  a 
small  amount  of  gas  and  the  largest  possible  yield  of  tar  (4  to  14 
per  cent)  .  This  is  brought  about  by  introducing  a  limited  and  care- 
fully regulated  quantity  of  air  and  steam,  sufficient  only  to  support 
partial  combustion.  The  same  method  is  always  followed  in  treat- 
ing pyrobituminous  shales,  on  account  of  the  greater  intrinsic  value 
of  the  tar,  of  which  5  to  25  per  cent  is  recovered.  These  processes 
approach  destructive  distillation  closely,  the  object  being  to  bring 
about  incipient  combustion  of  the  lignite  or  shale  and  the  non-con- 
densable gases  derived  therefrom,  thereby  raising  the  temperature 
sufficiently  to  cause  destructive  distillation. 

When  peat,  bituminous  coal  or  lignite  containing  a  large  propor- 
tion of  mineral  matter*  is  treated  in  a  producer,  it  is  always  intended 


286  GENERAL  METHODS  OF  PRODUCING  TARS  XIII 

to  produce  the  largest  possible  yield  of  gas,  and  the  smallest  pro- 
portion of  tar. 

PARTIAL  COMBUSTION  WITH  A  LIMITED  ACCESS  OF  AIR 

This  process  takes  place  in  manufacturing  generator  gas,  also 
upon  smelting  ores  in  blast-furnaces.  No  tar  is  produced  in  manu- 
facturing generator  gas,  hence  this  process  ceases  to  be  of  interest 
from  the  bituminologist's  standpoint.  In  the  case  of  blast-furnaces, 
no  tar  results  when  anthracite  coal  or  coke  is  used  as  fuel,  but  when 
bituminous  coal  is  used,  as  is  sometimes  the  practice  in  England  and 
on  the  Continent,  2  to  3*4  per  cent  of  its  weight  of  tar  is  produced. 
The  air  is  forced  into  the  blast-furnace  from  below,  and  travels 
upward  through  a  comparatively  thick  layer  of  incandescent  fuel. 
The  oxygen  on  coming  into  contact  with  the  fuel  is  first  converted 
into  carbon  dioxide,  which  on  rising  through  the  incandescent  layer 
combines  with  more  carbon,  forming  carbon  monoxide.  The  heat 
generated  volatilizes  a  certain  amount  of  the  bituminous  coal  in  the 
upper  layers  from  which  the  tarry  matters  escape  unconsumed. 

CRACKING  OF  OIL  VAPORS 

In  manufacturing  oil-gas,  crude  petroleum  or  a  heavy  distillate 
known  as  "gas-oil"  is  sprayed  under  more  or  less  pressure  into  a 
closed  retort  heated  to  redness.  This  causes  the  oil  to  decompose 
into  a  permanent  gas  and  from  5  to  10  per  cent  by  weight  of  oil-gas 
tar.  The  reaction,  known  as  "cracking,"  results  in  the  breaking 
down  of  the  hydrocarbons  present  in  the  petroleum  or  gas  oil  into 
simpler  substances. 

Water-gas  is  produced  by  the  combustion  of  anthracite  coal  or 
coke  in  an  atmosphere  of  steam  according  to  the  following  reaction  : 


The  gas  consists  theoretically  of  equal  volumes  of  carbon  monox- 
ide and  hydrogen.  It  burns  with  a  non-luminous  flame,  and  when 
intended  for  illuminating  purposes  must  be  enriched  or  "car- 
bureted." The  highly  heated  water-gas  as  it  is  generated,  is  ac- 
cordingly mixed  with  a  spray  of  crude  petroleum  or  gas  oil,  then 


XIII  CRACKING  OF  OIL  VAPORS  287 

passed  into  a  carburetor  in  which  the  oil  becomes  vaporized,  and 
finally  through  a  superheater  maintained  at  a  temperature  suffi- 
ciently high  to  crack  the  oil  vapors  into  permanent  gases.  From  2 
to  10  per  cent  of  tar  is  produced,  based  on  the  weight  of  the  petro- 
leum or  gas-oil  used.  This  tar  is  known  as  water-gas  tar  and  is 
similar  in  its  physical  and  chemical  properties  to  oil-gas  tar. 


CHAPTER  XIV 
WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH 

WOOD  TAR  AND  WOOD-TAR  PITCH 

This  chapter  will  deal  with  the  treatment  of  wood,  either  by 
destructive  distillation,  or  by  a  combination  of  steam  and  destruc- 
tive distillation.1  The  treatment  of  resinous  woods  by  the  steam 
distillation  process  alone,  for  the  recovery  of  turpentine  and  other 
oils,  does  not  fall  within  the  scope  of  the  present  treatise. 

Varieties  of  Wood  Used.  From  the  standpoint  of  destructive 
distillation,  woods  may  be  divided  into  two  classes,  viz.: 

Hard  Woods,  including  the  maple,  birch,  beech,  oak,  poplar, 
elm,  willow,  aspen,  alder,  ash,  hickory,  chestnut  and  eucalyptus. 

Resinous  or  Soft  Woods,  including  the  pine,  fir,  cedar,  cypress, 
spruce,  hemlock,  larch  or  tamarack. 

The  trees  from  which  hard  woods  are  obtained  are  known  as 
"broad-leaved"  or  udeciduous  trees,"  and  those  producing  resinous 
or  soft  woods  are  termed  "coniferous  trees"  or  "evergreens."  Soft 
woods  are  distinguished  from  hard  woods  principally  in  that  the 
former  contain  larger  quantities  of  turpentine  and  resin.  The  dis- 
tillation of  hard  wood  aims  at  the  recovery  of  wood  alcohol,  ace- 
tates, tar  and  charcoal,  whereas  the  distillation  of  resinous  wood 
(soft  wood)  is  directed  to  the  recovery  of  turpentine,  wood-tar 
oils,  tar  and  charcoal. 

In  the  wood-distilling  industry  the  basis  of  measurement  is  a 
cord,  which  is  taken  to  equal  128  cu.  ft.  of  the  closely  stacked  wood 
containing  15  per  cent  of  moisture.  The  weight  of  a  cord  varies 
with  different  kinds  of  wood,  from  about  1700  Ib,  in  the  case  of 
white  pine  and  poplar,  to  about  4000  Ib.  in  the  case  of  oak. 

For  purposes  of  destructive  distillation,  the  wood  should  be  as 
dry  as  possible,  since  during  the  process  all  the  moisture  must  be 
evaporated  before  the  wood  decomposes.  The  smaller  the  per- 
centage of  moisture  contained  in  the  wood,  the  more  rapid  will  be 
the  distillation  process  and  the  smaller  the  quantity  of  fuel  required. 

288 


XIV 


WOOD  TAR  AND  WOOD-TAR  PITCH 


289 


It  is  advisable  therefore,  to  cut  and  stack  the  green  wood  containing 
20  to  50  per  cent  of  moisture  from  six  months  to  two  years,  during 
which  the  moisture  content  will  fall  to  between  12  and  25  per  cent 
Yields  of  Distillation.  The  following  figures  will  give  a  general 
idea  of  the  average  yields  upon  distilling  a  cord  of  the  respective 
classes  of  wood: 


Hard  Woods 

Soft  (Resinous)  Woods 

Turpentine     

o 

5-  25  Gal.* 

Wood-tar  oils     

o 

30-  75  GaL 

Crude  -alcohol  (containing  acetone)  — 
Tar  

8-  12  Gal. 
8-  20  Gai 

2-    4  Gal. 
30-  60  GaL 

Charcoal  

40-  52  Bu. 

25-  40  Bu. 

ico-^co  Lb. 

50-100  Lb. 

*  Sawdust  yields  5  to  10  gal.  of  turpentine  and  light  wood  10  to  25  gal.  per  cord, 

The  tar  may  be  classified  according  to  the  type  of  carbonizing 
apparatus  employed,  as  follows:  mound  tar,  pit  tar,  oven  tar,  retort 
tar  and  generator  tar. 

Hard- Wood  Distillation.  The  following  figures  show  the  yields 
of  tar  and  charcoal  from  the  various  hard  woods  in  percentage, 
based  on  the  dry  weight  of  the  material : 2 


Tar, 
Per  Cent 

Charcoal, 
Per  Cent 

Hickory  

13.0 

37,7 

Maple  »  .  . 

12.8 

40.6 

Birch  

12.  0 

40,6 

Beech    

9.4. 

41  ig 

Oak  

7.8 

4$.  7 

Chestnut  

4.6 

47-6 

.A. 

In  the  United  States,  the  principal  centers  for  hard-wood  dis- 
tillation are  in  the  States  of  Pennsylvania,  New  York  and  Michigan. 
Soft-wood  distillation  is  carried  on  largely  in  the  States  of  Florida, 
Georgia,  North  and  South  Carolina  and  Alabama. 

The  crude  products  of  the  distillation  of  hard  wood  may  be 
grouped  into  four  classes,  viz. : 

(1)  Non-condensable  gases , 20-30  per  cent 

(2)  Aqueous  distillate  (crude  pyroligneous  acid) 30-50  per  cent 

(3)  Wood-tar  oils,  and  wood  tar 5-20  per  cent 

(4)  Charcoal > ; *  *O-45  per  cent 


290 


WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH 


XIV 


Method  of  Distilling.  When  hard  wood  is  heated  in  a  retort, 
water  passes  off  below  150°  C.,  after  which  decomposition  sets  in. 
With  soft  (resinous)  wood,  turpentine  and  water  commence  to 
distil  between  90  and  100°  C.  and  continue  to  150°  C.,  whereupon 
products  of  destructive  distillation  pass  over.  The  distillation  proc- 
ess is  practically  complete  at  430°  C.  In  the  case  of  hard  wood, 
the  first  group  of  products  which  pass  over  (between  150  to 
280°  C.)  include  acetic  acid,  methyl  alcohol  and  wood  creosote; 
the  second  group  (280  to  350°  C.)  consist  of  non-condensable  gases 
(about  53  per  cent  of  carbon  dioxide,  38  per  cent  of  carbon  monox- 
ide, 6  per  cent  of  methane,  3  per  cent  of  nitrogen,  etc.)  ;  the  third 
group  (350  to  400°  C.)  are  composed  of  solid  hydrocarbons  and 
their  derivatives.  The  yields  of  methyl  alcohol  and  acetic  acid  in- 
crease with  a  rise  of  temperature  up  to  300°  C.  beyond  which  they 
decrease;  moreover  their  yield  is  greater  when  the  wood  is  heated 
slowly,  than  when  the  distillation  is  forced. 

The  following  fractions  are  obtained  on  distilling  beech-wood 
tar  (specific  gravity  at  15°  C.  1.05-1.10) : 

Aqueous  distillate  (*) 15-20  per  cent 

Light  tar  oils  (to  110°  C.) 5-10  per  cent  (sp.  gr.  o.  90-0. 98) 

Heavy  tar  oils  (120-270°  C.) 10-20  per  cent  (sp.  gr.  i  .04-1 .05) 

Soft  wood-tar  pitch 40-60  per  cent 

*  Containing  10  per  cent  acetic  acid  and  3-5  per  cent  crude  wood  alcohol. 

In  distilling  hard  woods, 
large  rectangular  iron  retorts 
are  used,  measuring  6  ft  in 
width,  7  ft.  high  and  either  27 
or  50  ft.  long,  depending  upon 
whether  they  are  intended  to 
hold  2  or  4  carloads.  The  re- 
torts are  set  in  brickwork,  and 
provided  with  large  air-tight 
iron  doors  at  the  ends.  The 
wood  is  loaded  on  small  iron 
cars  holding  between  I  and  3 
cords  each  (Fig.  91)  which 

are  run  on  tracks  directly  into  the  retorts. 

The  arrangement  of  a  modern  wood-distilling  plant  is  shown  in 

Fig.  92;  where  A  represents  a  car;  5,  the  retort;  C,  first  cooler;  JD, 


FIG.  91.— Iron  Cars  Used  in  the  Distilla- 
tion of  Hardwood. 


XIV 


HARD-WOOD  DISTILLATION 


291 


second  cooler;  E9  the  acetate  drying  floor;  a,  condensers;  b.  liquor 
trough;  c}  gas  main  to  boilers;  i,  fuel  conveyor;  w,  fireplace;  w,  ash 
pit;  o,  hinged  spout  to  deliver  fuel  from  i  to  m.  After  the  retort 
is  charged,  the  doors  are  closed  and  heat  applied  slowly,  either  by 


FIG.  92.— Modern  Wood  Distilling  Plant. 


FIG,  93.—  Plant  for  Refining  Wood  Tan 


burning  the  non-condensable  gases  resulting  from  the  distillation 
process,  or  by  atomizing  the  tar  underneath  the  retort  with  a  jet  of 
steam.  Unless  the  gases  are  stored  in  a  gas-holder,  the  process  is 
started  by  burning  a  small  amount  of  wood  on  an  auxiliary  grate 
beneath  the  retort. 


292 


WOOD  TAR,  WQOto-fAR  PlTCti  AND  ROSIN  PITCH 


XIV 


The  vapor  from  the  retort  is  passed  through  condensers,  where 
the  pyroligneous  acid,  alcohol  and  other  condensable  constituents 
are  recovered.  These  are  conveyed  to  large  settling  tanks,  and  al- 
lowed to  rest  quietly  until  the  tar  settles  out 

The  distillation  process  continues  from  twenty  to  thirty  hours, 
whereupon  the  fires  are  extinguished  and  the  retort  allowed  to  cool. 
The  small  iron  cars  now  carrying  charcoal  are  quickly  run  from  the 
retort  into  large  iron  coolers,  similar  in  size  and  shape  to  the  retort 
itself,  and  the  doors  are  closed  to  prevent  access  of  air. 

Refining  Processes.  The  general  arrangement  of  a  refining 
plant  is  shown  in  Fig.  93,  where  A  1—2  represents  the  raw  liquor 
vats,  B  1—5  represent  the  raw  liquor  settling  tanks,  C  i  the  tar 
still,  C  2—3  the  raw  liquor  still,  D  1-2  the  neutralizing  vats, 
E  1—3  the  lime-lee  stills,  F  1—3  the  alcohol  stills,  G  the  weak  alcohol 
storage  tank  and  H  the  strong  alcohol  storage  tank.  Table  XVII 
shows  a  diagrammatic  outline  of  the  products  obtained  upon  distill- 
ing hard  wood,  and  refining  its  distillates. 

TABLE  XVII 

HARD  WOOD 

Distilled  Destructively 


Non-condensable  Gases 
(Burned  under  retort) 


Condensable  Distillate 
Separated  by  settling  into: 


Charcoal  Residue 


Crude  Aqueous  Portion 
Separated  by  distillation  into: 

i 

Raw  Tar 
Distilled  into: 
1 

i'                                          I 
Distillate,  known  as                  Tarry  Residue 

Distillate  of 

I 
Residue  of 
Boiled  Tar 
^  Redistilled 

KfoiitrnliTiwl  with  Hm*»  nnrl  rliVfillorl                  ^^li—  _  *.»  » 

»» 

1 

1 

illate  composed  of    Residue  composed  of  crude 
Tude  dilute  wood       acetate  of  lime.  Converted 

i          i          i 

Light  oil      Heavy  oil         Residue  of 
Wood-tar  pitch 

alcohol  containing 
acetone.  Rectified 
into: 


by  roasting  into  gray  acetate 
of  lime.  Then  treated  by 
one  of  the  following  methods 


11      A 

Acetone    Wood  alcohol     Distilled  with     G 
Sulf  uric  acid        o 

mverted  into 
ther  acetates 

0 
Distilled  at  a  high 
temperature  alone 

.         i, 

1 

1               i 

I              i 

Distiflate  of 

Residue  of 

Other 

Acetone       Light 

Heavy     Residue  of 

Acetone 

Calcium 

Acetates 

Acetone 

Acetone      Calcium 

Sulfate 

Oils 

Oils       Carbonate 

XIV  HARD-WOOD  DISTILLATION  293 

After  the  pyroligneous  acid  and  tar  have  been  separated  by  set- 
tling, the  crude  products  are  distilled  independently  to  recover  any 
pyroligneous  acid  from  the  crude  tar,  and  conversely,  any  tar  re- 
tained by  the  crude  pyroligneous  acid  (dissolved  in  the  alcohol  and 
acetone  present).  The  method  consists  in  heating  the  tar  with 
steam  in  closed  coils  until  the  water  is  driven  off,  and  then  blowing 
live  steam  thrpugh  the  charge.3 

A  continuous  process,  known  as  the  "Badger-Stafford  Process,"  4 
has  been  devised  for  treating  scrap  wood  obtained  in  other  manu- 
facturing operations.  The  hogged  scrap  wood  (averaging  70  per 
cent  maple,  25  per  cent  birch  and  5  per  cent  ash,  elm  and  oak)  is 
first  passed  through  six  rotary  driers  heated  by  flue  gases  entering 
at  600°  F.  The  scrap  wood  is  discharged  from  the  driers  at  302°  F. 
and  then  fed  into  retorts  40  feet  high  and  10  feet  in  diameter.  Air- 
tight valves  at  the  top  and  bottom  allow  the  introduction  of  the 
wood  and  the  removal  of  the  charcoal,  respectively,  without  escape 
of  gas,  which  passes  off  at  the  top  of  each  retort  to  four  condensers 
mounted  around  it.  The  average  temperature  in  the  central  zone  is 
950°  F.,  and  at  the  bottom  490°  F. 

The  products  from  the  retorts  are  charcoal,  which  is  passed  to 
coolers  and  conditioners;  pyroligneous  acid  or  "green  liquor,"  which 
is  pumped  from  the  condensers  to  the  primary  separators;  and  non- 
condensable  gas,  which  is  used  for  heating  the  retorts  and  burned 
under  the  boilers. 

Each  ton  of  wood  produces  1 1 1  gal.  of  pyroligneous  acid  con- 
taining approximately  4.5  per  cent  methanol  and  12.5  per  cent  acetic 
acid,  also  allyl  alcohol,  acetone,  methyl  acetate,  suspended  and  dis- 
solved tar,  various  oils  and  water.  The  pyroligneous  acid  is  first 
delivered  to  settling  tanks  where  the  suspended  tar  is  largely  re- 
moved, and  then  pumped  to  the  primary  tar  stills.  The  acid  distil- 
late from  these  stills  is  returned  to  the  settling  tanks,  while  the  dis- 
tilled heavy  tar  is  sent  to  the  pitch  still,  where  creosote  oil  and  pitch 
are  recovered  by  distillation  under  a  vacuum  of  27  inches  with  the 
use  of  steam  at  125  Ib.  pressure. 

The  pyroligneous  acid  free  of  settled  tar  is  distilled  in  six  large 
batch  primary  stills  operating  on  a  30  hour  cycle.  The  soluble  tar 
remaining  as  a  residue  in  these  stills  is  pumped  under  the  boilers 
where  it  is  burned.  The  acid  distillate  passes  to  a  separator  where 


294 


WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH 


XIV 


the  acid  oils  are  removed,  then  through  a  sand  filter,  and  finally  to 
the  continuous  stills,  which  yield  crude  95  per  cent  methanol  at  the 
top  of  thg  column  and  15  per  cent  acetic  acid  at  the  bottom.  The 
crude  methanol,  which  contains  allyl  alcohol,  acetone,  methyl  acetate 
and  alcohol  oils,  is  first  fractioned  in  two  discontinuous  stills,  which 
yield  refined  allyl  alcohol  and  alcohol  oils  as  final  products,  while 
a  50  per  cent  methyl  acetone,  an  intermediate  methyl  acetate,  and  a 
99  per  cent  methanol  are  sent  to  the  four-column  continuous  stills, 
which  in  turn  yield  75  per  cent  methyl  acetone,  75  per  cent  methyl 
acetate  and  C.P.  methanol. 

The  15  per  cent  acetic  acid  obtained  from  the  first  continuous 
de-alcoholizing  distillation  is  used  directly  in  the  production  of 
ethyl  acetate  from  ethyl  alcohol  in  the  presence  of  sulfuric  acid. 

A  flow-sheet  of  the  process  is  illustrated  in  Table  XVIII. 

TABLE  XVIII 

FROM  CARBONIZATION  BUILDING 


\ 

> 

;L 

H 

CRUDE  METHANOL 

L 

ETHYL  ALCOHOL 

I    |               PLUS  LIME               | 

H 

ETHYL  FORMATE 

H 

*j     WEAK  ACETIC  ACID 

PLUS  CALCIUM  CLORIDE       ' 

H 

IPLUS  SULPHURIC  ACID  1     |  CRUDE  ETHYL  ACETATE   |     ^{ 

|             PLUS  LIME 

|      DRY  ETHYL  ACETATE      f*^ 

H 

J" 

HEAVY  ACID  OIL 

L 

r 

ALLYL  ALCOHOL 


FINISHED  KETONES 


1WASHED  ALCOHOL  OIL 


HIGH  BOILING  ESTERS 


85%  ETHYL  ACETATE 


•|   HEAVY  NEUTRAL  01  L" 


LIGHT  ACID  OIL 


The  following  table  gives  the  yields  of  the  various  intermediate 
and{inal  products  per  ton  of  dried  wood  treated: 


INTERMEDIATE  PRODUCTS 


Total  100%  spirits,  gallons. . 


FINAL  PRODUCTS 

Charcoal,  Ibs 600 

Non-condensable  gas,  cubic  feet   (290 

B.t.u.  per  cubic  foot) 5000 

5,0       C,  P.  methanol,  gallons 3.118 

Methyl  acetone,  gallons o.  653 

Allyl  alcohol,  gallons o. 048 

Ketones,  gallons 0.126 

Methyl  acetate,  gallons o. 945 

Soluble  tar,  gallons 22.0 


XIV 


SOFT-WOOD  DISTILLATION 


295 


Settled  tar,  gallons n  .o 

Acetic  acid  (as  100%),  Ibs 101 .0 


Pitch,  Ibs 66.0 

Creosote  oil,  gallons 3.25 

Ethyl  acetate,  gallons. 14-65 

Ethyl  formate,  gallons i .  27 


Various  other  processes  have  been  devised  for  distilling  wood 
waste  in  the  production  of  wood  tar  involving  the  treatment  of 
sawdust,  shavings,  splittings,  wood  bark,  roots,  refuse  of  one  kind 
or  another.5 

The  dehydrated  tar,  known  as  "boiled  tar"  or  "retort  tar," 
amounting  to  between  3  and  10  per  cent  of  the  weight  of  the  wood, 
may  be  utilized  in  one  of  the  following  ways: 

( i )    It  may  be  sold  as  such,  and  used  for  preserving  wood. 

?  2 )    It  may  be  burned  under  the  retorts  as  fuel. 

(3)  It  may  be  subjected  to  fractional  distillation  to  recover  the 
light  oils  boiling  below  150°  C,  heavy  oils  boiling  between  150° 
and  240°  C.,  and  the  residual  pitch  constituting  between  50  and  65 
per  cent  by  weight  of  the  tar.  The  light  oils  are  used  as  solvents  in 
manufacturing  varnish,  and  the  heavy  oils  after  further  refining  are 
marketed  as  commercial  wood  creosote  which  finds  a  sphere  of  use- 
fulness as  a  disinfectant,  wood  preservative,  and  flotation  oil. 

Soft  (Resinous)  Wood  Distillation.  Method  of  Distilling.  In 
treating  soft  wood  (resinous  wood  )a  different  method  is  followed. 
Iron  or  steel  retorts  varying 
in  capacity  from  one  to  four 
cords  are  used,  constructed 
either  vertically  or  horizon- 
tally, as  shown  in  Fig.  94. 
Low  -  pressure  superheated 
steam,  or  saturated  steam  un- 
der high  pressure,  is  intro- 
duced into  the  retort  to  re- 
move the  turpentine,  and  then 
the  volatile  oils  (known  as 
"heavy  oils")  leaving  a  resi- 
due of  coke  behind.  Three  classes  of  resinous  wood  are  used  for 
the  purpose: 

( I )  "Light  wood"  containing  comparatively  large  quantities  of 
turpentine. 


FlG.  94. — Retorts  for  Distilling  Soft  Wood. 


296  WOOD  TAR,  tPOOD-TAR  PITCH  AND  ROSIN  PITCH  XlV 

"Stumps/'  which  also  contain  more  or  less  turpentine 
Saw-mill  waste,  which  is  rather  poor  in  turpentine. 

The  wood  is  first  "hogged/*  or  in  other  words,  cut  into  chips 
before  it  is  introduced  into  the  retort.  The  temperature  is  raised 
gradually  to  200°  C.  as  the  steam  passes  through  the  retort  Water 
and  crude  turpentine  distil  over  first  and  are  separated  by  settling. 
As  the  temperature  rises  above  200  to  220°  C.  the  wood  commences 
to  decompose  into  tarry  substances,  and  at  about  250°  C.  the  resins 
present  break  up  into  "rosin  spirits"  and  "rosin  oils,"  Both  the 
crude  turpentine  and  the  heavy  oils  are  redistilled  separately,  the 
former  producing  purified  wood  turpentine  and  the  latter  pine  oil, 
rosin  oil  and  pitch.  Rosin  spirits  boils  between  80  and  200°  C, 
wood  turpentine  between  150  and  180°  C.,  pine  oil  between  190 
and  240°  C,  and  rosin  oil  between  225  and  400°  C.  This  process 
is  illustrated  diagrammatically  in  Table  XIX. 

TABLE  XIX 

LIGHT  WOOD  (PINE  OR.  RESINOUS  WOODS) 
Steam  distilled  up  to  200°  C.,  and  then  distilled  destructively 

Water  Below  200°  C,  Above  aoo°  C. 

Condensable  Distillate.    Redistilled  into:  Destructive  distillation  occurs 


I  I  |  I  i 

Light  oils  Heavy  oils  Non-condensable      Condensable        Charcoal 

(Fractioned)  (Fractioned)  gases  Distillate  Residue 


|  J ^  J  J  I  Treated  the  same  as  in 

Rosin        Wood         Part  of      Balance  of     Rosin     Pine-tar  Hard  wood  distillation 

Spirits    Turpentine     Pine  oil       Pine  oil         oils         pitch  (See  Table  XVII) 

In  some  cases  the  "light  wood"  is  subjected  to  a  process  of 
destructive  distillation  without  using  steam.  The  temperature  is 
raised  slowly  and  the  distillate  under  200°  C,  caught  separately  to 
avoid  contamination  with  tarry  matters.  After  the  temperature 
rises  above  200°  C.,  the  process  follows  the  same  course  as  for  hard- 
wood distillation. 

Refining  Processes.  The  distillate  under  200°  C.  is  fractioned 
into  light  and  heavy  oils  respectively.  The  light  oil  is  in  turn  redis- 
tilled to  recover  the  rosin  spirits,  wood  turpentine  and  a  part  of  the 


XIV  SOFT -WOOD  DISTILLATION  2&7 

pine  oil.  The  heavy  oil  is  similarly  redistilled  to  separate  the  pine 
oil,  rosin  oil  and  a  part  of  the  pitch.  The  crude  tar  obtained  above 
200°  C,  is  distilled  to  recover  any  acetic  acid,  and  the  residue  either 
marketed  as  "pine  tar"  or  distilled  to  separate  the  light  and  heavy 
oils  from  the  pine-tar  pitch  obtained  as  residue.  A  pitch-like  prod- 
uct may  be  obtained  upon  blowing  rosin  oil  with  air  and  superheated 
steam.8 

Another  treatment  of  soft  wood  consists  in  subjecting  it  to  an 
extraction  process  with  solvents,  which  are  recovered  and  used  over 
again.  In  this  process,  the  wood  is  first  ground  into  small  frag- 
ments, which  may  either  be  treated  as  such,  or  else  subjected  to  a 
treatment  with  live  steam  to  remove  the  volatile  foils,  including  the 
turpentine  and  pine  oil.  The  rosin  is  extracted  with  hot  petroleum 
naphtha  or  benzol.  The  extract  is  thereupon  distilled  to  remove 
the  solvent  (also  the  turpentine  and  pine  oil,  where  the  wood  was 
extracted  directly,  without  steaming).  The  rosin  is  extracted  from 
the  residue  by  means  of  a  petroleum  solvent  (sometimes  after  first 
purifying  by  dissolving  In  furfural  and  subsequent  evaporation), 
leaving  a  form  of  wood  pitch  which  tests  as  follows : 

(Test  15^)  Fusing-point  (R,  and  B.  method) 195-240°  F. 

(Test  23)    Soluble  in  88°  petroleum  naphtha 10-20  per  cent. 

(Test  370)  Acid  value 11-115 

(Test  $jd)  Saponification  value 140-170 

(Test  37*)  Saponifiable  constituents 9*-95  per  cent. 

The  wood,  after  treatment  in  this  manner,  may  either  be  distilled 
destructively,  or  used  as  a  fuel,  or  used  as  a  filler  in  other  manufac- 
turing operations, 

Wood  Tars,  The  bituminous  products  derived  from  the  de- 
structive distillation  of  wood  are  designated  commercially  as  hard- 
wood tar  and  pine  tar ;  hard-wood-tar  pitch  and  pine-tar  pitch. 

Wood  tar  has  also  been  termed  "Stockholm  tar"  and  "Arch- 
angel tar." 

Hard-wood  Tar  and  Pine  Tar.  The  physical  and  chemical 
characteristics  of  the  tars  and  corresponding  pitches  vary,  depend- 
ing upon  the  kind  of  wood  used,  as  well  as  the  exact  method  of 
treatment  The  following  figures  will  give  a  general  idea  of  the 


208  WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH  XIV 

characteristics  of  the  dehydrated  hard-wood  tar  and  pine  tar  ordi- 
narily encountered  in  the  American  market : 

HARDWOOD         PINE  TAR  (FROM 
TAR  RESINOUS  WOODS) 

.(Test   i)    Color  in  mass ..Black  Brownish 

(Test   7)    Specific  gravity  at  77°  F i .  10-1 , 30  i , 05-1 . 10 

(Test    8)    Viscosity Fairly  liquid  Viscous 

(Test   9)     Consistency  at  77°  F Liquid  Liquid 

(Test  15)    Fusing-point.  U Below  20°  F.  Below  50°  F. 

(Test  1 6)    Volatile  matter  at  500°  F.,  5  hrs. . ,  35-60  per  cent  40-7  5  per  cent 

(Test  170)  Flash-point 5°-75°  F-  60-90°  F. 

(Test  19)    Fixed  carbon 5-  ao  per  cent  5-  15  per  cent 

(Test  ai)    Solubility  in  carbon  disulfide 95-100  per  cent  98-100  per  cent 

Non-mineral  matter  insoluble o-    5  per  cent  o-    2  per  cent 

Mineral  matter o-    i  per  cent  o-    x  per  cent 

(Test  22)    Carbines o-    2  per  cent  o-    2  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha   50-  90  per  cent  65-  95  per  cent 

(Test  28)    Sulfur o.o  per  cent  o.o  per  cent 

(Test  30)    Oxygen 2-10  per  cent  5-10  per  cent 

(Test  32)    Naphthalene None  None 

(Test  33)    Solid  paraffins None  None 

(Test  34*)  Sulfonation  residue Trace  to  5%  Trace  to  $% 

(Test  37*)  Saponifiable  constituents 25-85%  20-60% 

(Test  37jr)  Resin  acids Up  to  15%  Up  to  30% 

(Test  39)    Diazo  reaction Yes  Yes 

(Test  40)    Anthraquinone  reaction No  No 

(Test  41)    Liebermann-Storch  reaction Yes  Yes 

According  to  David  Holde,  on  shaking  wood  tar  with  water, 
the  aqueous  extract  will  react  acid  (due  to  the  acetic  acid  present), 
and  upon  adding  a  few  drops  of  ferric  chloride,  will  at  first  form  a 
green  and  then  a  bluish-  to  brownish-green  coloration.  Birch-bark 
tar  gives  a  green  color  with  ferric  chloride,  which  on  addition  of 
ammonia  changes  to  an  intense  blue ;  whereas  birch  tar  gives  a  brown 
color.  Both  hard-wood  tar  and  pine  tar  are  almost  completely 
soluble  in  absolute  alcohol,  glacial  acetic  acid  and  acetic  anhydride. 
On  subjecting  wood  tar  to  distillation,  the  first  portion  passing  over 
shows  3,  separation  of  water  which  will  react  acid.  On  continuing 
the  4*stiMati°n>  oily  matters  are  obtained  which  dissolve  readily  in 
alcohol,  and  on  treatment  with  concentrated  sulfuric  acid  become 
converted  into  wate^-soluble  substances.  Pine  tar  has  a  high  acid 
value,  since  it  often  contains  as  much  as  30  per  cent  by  weight  of 
res}n  acids,  and  is  characterized  by  the  absence  of  sulfur,  paraffins, 
naphthalene  and  anthracene;  and  by  the  presence  of  phenol  (Test 
39)  and  resin  acids  (Test  41)  which  causes  it  to  have  a  high  acid 
value  (Test  374)  and  give  an  acid  reaction  to  litmus. 


XIV                                         WOOD-TAR  PITCHES  299 

The  following  constituents  have  been  identified  in  German  tars : T 

BEECHWOOD  PINE 

TAR  TAR 

Per  Cent  Per  Cent 

Unsaponifiable  matter 18.0  53.5 

Saponifiable  matter: 

Hydroxy  acid  anhydrides 9.5  o.o 

Hydroxy  acids 52.3  14.0 

Resin  acids 7.7  17.0 

Reported  as  fatty  acids* 3.2  6.0 

Phenols 9.3  9.5 


Total 100,0  loo. o 

*  Separated  by  TwitchelTs  method,  but  not  true  fatty  acids. 

Wood-tar  Pitches.  Hard-wood-tar  pitch  and  f>ine-tar  pitch  vary 
in  their  physical  properties,  depending  upon  the  following  cir- 
cumstances : 

1 i )  The  variety  of  wood  used. 

(2)  The  method  by  which  the  wood  is  distilled,  including  the 
temperature,  its  duration,  the  kind  of  retort,  etc, 

(3)  The  extent  to  which  the  tar  is  distilled  in  producing  the 
pitch.    The  further  it  is  distilled,  the  harder  will  be  the  pitch  and  the 
higher  its  fusing-point. 

Hardwood-tar  Pitch  and  Pine-tar  Pitch.  These  comply  with 
the  following  characteristics  : 

PINE-TAR  PITCH 

HARDWOOD-TAR  (FROM  RESINOUS 
PITCH  WOOD) 

(Test    i)    Color  in  mass Black  Brownish  black 

(Test   2)    Homogeneity Uniform  Uniform 

(Test   4)    Fracture Conchoidal  Conchoidal 

(Test    5)    Lustre Bright  to  dull  Bright  to  dull 

(Test    6)    Streak Brown  to  black  Brown 

(Test   7)    Specific  gravity  at  77°  F i ,  20-1 .30  1 , 10-1 . 15 

(Test   gb)  Penetration  at  77°  F 0-60  0-60 

(Test   gc)  Consistency  at  77°  F 10-100  10-100 

(Test   9</)  Susceptibility  index >  ico  >  100 

(Test  10)    Ductility Variable  Variable 

(Test  1 50)  Fusing-point  (K.  and  S.  method)..  100-000°  F,  100-000°  F, 

(Test  15^)  Fusing-point  (R.  and  B.  method). .  1 15-005°  P.  115-005°  F, 

(Test  1 6)    Volatile  matter Variable v  Variable 

(Test  19)    Fixed  carbon I5~35  PC*  cent  10-05  per  cent 

(Test  01)    Soluble  in  carbon  disulfide 3°-95  per  cent  40-95  per  cent 

Non-mineral  matter  insoluble 5-70  per  cent  0-60  per  cent 

Mineral  matter , o-i  per  cent         0*1  per  cent 


800  WOOD  TAR,  WOOD»TAR  PITCH  AND  ROSIN  PITCH  XIV 

PINE-TAR  PITCH 

HARDWOOD-TAR  (FROM  RESINOUS 
PITCH  WOOD) 

(Test  aa)    Carbenes 2-10  per  cent  0-5  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha  1 5-50  per  cent  25-80  per  cent 

(Test  28)    Sulfur o  per  cent  o  per  cent 

(Test  30)    Oxygen  in  non-mineral  matter —     1-5  per  cent  2-8  per  cent 

(Test  32)    Naphthalene None  None 

(Test  33)    Solid  paraffins. None  None 

(Test  340)  Sulfonation  residue 0-5  per  cent  0-3  per  cent 

(Test  37*)  Saponifiable  constituents 60-95  per  cent  45-75  per  cent 

(T$st37£)  Resin  acids Up  to  20  per  cent  Up  to  40  per  cent 

(Test  39)    Diazo  reaction Yes  Yes 

(Test  40)    Anthraquinone  reaction No  No 

(Test  41)    Liebermann-Storch  reaction Yes  Yes 

The  following  constituents  have  been  identified  in  German 
pitches : 8 

HARD  BEECHWOOD-  MEDIUM  HARD 

TAR  PITCH,  PINE-TAR  PITCH, 

Per  Cent  Per  Cent 

Unsaponifiable  matter 6.0-    6.3  19.7 

Saponifiable  matter: 

Hydroxy  acids  and  anhydrides 77«o-  65 .3  31 . 8 

Resin  acids o.o-    o.o  35.2 

Neutral  tar  resins 14.0-  25.4  1.5 

Reported  as  fatty  acids  * 1.5-    1.5  a. 8 

Phenols 1.5-    1.5  8.0 

Mineral  matter o.o-    o.o  I  .o 

Total 100. o  100,0  100,0 

*  Separated  by  TwitchelTs  method,  but  not  true  fatty  adds. 

V 

Soft  and  medium  hard  wood-tar  pitches  are  fairly  soluble  in 
ethyl  alcohol,  and  as  the  hardness  increases  the  solubility  decreases. 
Hard  pitches  are  only  sparingly  soluble. 

According  to  Benson  and  Davis,9  wood-tar  pitches  are  more 
soluble  in  acetone  than  in  carbon  disulfide.  Thus,  hardwood-tar 
pitches  were  found  to  be  15.6—31.9  per  cent  more  soluble  in  acetone 
than  in  carbon  disulfide,  and  pine-tar  pitches  (obtained  from  the 
Douglas  fir)  8.0  to  57.8  per  cent  more  soluble  in  the  former  solvent. 

Wood-tar  pitches  are  characterized  by  their  extreme  suscepti- 
bility to  changes  in  temperature,  by  the  fact  that  they  appear  hard 
and  at  the  same  time  show  a  surprisingly  low  fusing-point,10  and  are 
characterized  by  the  absence  of  sulfur,  paraffins,  naphthalene  and 
anthracene.  Wood-tar  pitches  are  notoriously  non-weatherproof. 
They  are  extremely  susceptible  to  oxidation  on  exposure  to  the 
weather  and  are  soon  converted  into  a  lifeless  and  pulverulent  mass. 


XIV  ROSIN  PITCH  301 

However,  their  physical  properties  and  weather-resistance  may  be 
improved  by  fluxing  with  cashew-nut-shell  oil,11  or  by  blending  with 
fatty-acid  pitch,  which  latter  may  be  accomplished  by  heating  to- 
gether pitches  of  the  same  fusing-points,  respectively,12 

Wood  tar  may  be  hardened  and  made  more  suitable  for  use  in 
black  paints  by  treating  with  concentrated  sulfuric  acid  removing 
the  water-soluble  substances,13  and  the  product  may  be  dissolved 
in  acetone  or  methyl  alcohol  for  use  as  lacquers.14  Artificial 
resins  may  also  be  produced  by  treating  wood  tar  with  formaldehyde 
in  the  presence  of  a  catalyst,15  or  by  heating  wood  tar  with  10  per 
cent  zinc  oxide  at  110°  C.,16  or  by  treatment  with  chlorine  in  the 
presence  of  A1C13  as  catalyst,17  in  which  latter  case  the  product  is 
soluble  in  methyl  alcohol.  Wood  tars  may  be  hardened  by  heating 
with  sulfur,18  or  by  blowing  with  air  in  the  presence  of  a  small 
amount  of  sulfur,19  or  by  blowing  with  air,  ozonized  air  or  oxygen 
at  120-150°  C20 

Wood  tars  have  been  utilized  for  the  production  of  tar  soaps, 
lubricants,  flotation  agents,  pharmaceutical  products,  etc.21 

ROSIN  PITCH 

Raw  Materials  Used.  The  sap  of  the  long-leaf  pine,  known 
chemically  as  an  oleo-resin,  is  composed  of  a  mixture  of  spirits  of 
turpentine  and  rosin.  It  is  gathered  by  incising  the  bark  one-half  to 
one  inch,  whereupon  the  oleo-resin  slowly  exudes  and  is  collected  in 
small  cups. 

The  oleo-resin  is  then  distilled  to  separate  the  spirits  of  turpen- 
tine from  the  rosin.  The  apparatus  ordinarily  used  in  the  United 
States  for  this  purpose  is  shown  in  Fig.  95,  consisting  of  a  simple 
type  of  copper  still  with  a  "worm"  condenser.  The  capacity  of  the 
still  varies  from  10  to  40  barrels,  and  usually  between  15  and  20, 
After  the  still  is  charged,  the  fire  is  started,  and  a  mixture  of  spirits 
of  turpentine  and  water  (since  the  oleo-resin  contains  between  5 
and  10  per  cent  of  water)  appears  in  the  condenser.  When  all  the 
water  has  boiled  over,  additional  quantities  are  added  in  a  small 
stream  during  the  distillation,  since  the  introduction  of  water  causes 
the  turpentine  to  boil  at  a  lower  temperature  and  prevents  over- 
heating, improving  both  the  color  and  yield  of  the  turpentine  and 
rosin.  Towards  the  end  of  the  distillation  the  stream  of  water  is 


302 


WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH 


XIV 


shut  off,  and  the  rosin  heated  until  all  the  moisture  is  expelled, 
usually  between  300  and  400°  F.  Before  cooling,  any  foreign  mat- 
ter is  skimmed  off  the  surface  of  the  rosin,  after  which  it  is  strained 
through  a  fine  mesh  screen  and  barreled,22 

Method  of  Distilling.  Rosin,  deprived  of  its  turpentine,  when 
heated  in  a  closed  retort  undergoes  destructive  distillation,  yielding 
a  gas,  an  aqueous  liquor  'and  an  oily  distillate  which  may  be  sepa- 
rated into  several  fractions.  If  the  process  is  carried  to  completion, 
coke  will  be  left  as  residue.  If  the  distillation  is  terminated  before 
the  formation  of  coke,  a  pitchy  residue  will  remain,  known  com- 
mercially as  "rosin  pitch." 

The  rosin  may  be  distilled  either  with  or  without  superheated 
steam.  If  the  latter  is  employed,  the  quality  of  the  distillate  is  im- 


FIG.  95. — Retort  for  Distilling  Rosin. 


proved,  and  a  much  better  temperature  control  obtained.  Distilla- 
tion under  vacuum  is  also  used  in  many  cases.  The  rosin  may  ac- 
cordingly be  distilled  by  any  of  the  following  processes : 

( i )   At  atmospheric  pressure  without  steam. 
(2)*  With  superheated  steam. 
(3)  Under  vacuum. 

When  the  temperature  of  the  rosin  reaches  150°  C.  a  liquid 
distillate  appears  which  separates  into  two  layers,  the  lower  con- 
taining acetic  acid,  also  other  organic  acids  dissolved  in  water,  and 
the  upper  composed  of  oily  substances  known  as  urosin  spirits"  or 
"pinoline."  When  the  temperature  reaches  200°  C.  the  receiver  is 
changed,  and  the  distillate  which  ensues  is  either  collected  together 
or  separated  into  fractions.  The  temperature  of  the  residue  in  the 
retort  is  permitted  to  reach  350  to  360°  C.  but  never  to  exceed  the 
latter.  The  distillate  between  200  and  360°  C.  known  as  "rosin 
oil.*1  mav  be  separated  into  various  fractions  termed  "yellow  rosin 


XIV  ROSIN  PITCH  303 

oil,"  "blue  rosin  oil,"  "green  rosin  oil,"  etc.,  depending  upon  their 
respective  colors. 

Products  Obtained.  In  distilling  rosin  destructively  at  atmos- 
pheric pressure,  the  following  products  are  separated: 

Non-condensable  gases 9.0  per  cent 

Acid  liquor 3.5  per  cent 

Rosin  spirits  or  pinoline 3.5  per  cent 

Rosin  oil 67.0  per  cent 

Rosin  pitch 16.0  per  cent 

Loss  (rosin  adhering  to  walls  of  still,  etc.) i  .o  per  cent 

According  to  Victor  Schweizer,23  when  rosin  is  distilled  with 
superheated  steam,  the  following  yields  are  obtained: 

Acid  liquor 5.5-  5. 8  per  cent 

Rosin  spirits 1 1 . 25-12 .  o  per  cent 

Blue  rosin  oil 49 ,o  -50. 5  per  cent 

Brown  rosin  oil 10 . 25-10. 65  per  cent 

Rosin  pitch 18.0  -19.0  per  cent 

The  rosin  pitch  is  run  from  the  still  while  it  is  hot,  and  allowed 
to  cool  in  a  suitable  receiver, 

Properties  of  Rosin  Pitch.  It  is  fairly  uniform  in  composition 
and  conforms  with  the  following  characteristics : 

(Test    i)    Color  in  mass Black 

(Test    2)    Homogeneity Uniform 

(Test   4)     Fracture Conchoidal 

(Test    5)    Lustre Dull 

(Test    6)    Streak Light  yellow  to  brown 

(Test    7)     Specific  gravity  at  77°  F i  .08-1 .15 

(Test    9^)  Penetration  at  77°  F 0.5  ^ 

(Test    9^)  Consistency  at  77°  F 50-100 

(Test    gd)  Susceptibility  index Greater  than  100 

(Test  iof)  Ductility  at  77°  F o 

(Test  i$a)  Fusing-point  (K.  and  S.  method) 120-200°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 135-225°  F. 

(Test  16)    Volatile  matter,  500°  F.,  5  hrs 10-18  per  cent 

(Test  17)    Flash-point Above  250°  F. 

(Test  19)    Fixed  carbon 10-  20  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 98-100  per  cent 

Non-mineral  matter  insoluble * o-    2  per  cent 

Mineral  matter o-    i  per  cent 

(Test  22)     Carbenes o-    5  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha 90-100  per  cent 

(Test  28)    Sulfur o.o  per  cent 

(Test  30)    Oxygen  in  non-mineral  matter 5-10  per  cent 

(Test  33)     Solid  paraffins o.o  per  cent 

(Test  340)  Sulfonation  residue 0-5  per  cent 

(Test  37*)  Saponifiable  constituents 25-95  per  cent 

(Test  39)    Diazo  reaction Yes 

(Test  40)    Anthraquinone  reaction No 

(Test  41)    Liebermann-S torch  reaction Yes 


304  WOOD  TAR,  WOOD-TAR  PITCH  AND  ROSIN  PITCH  XIV 

Rosin  pitch  is  very  much  like  rosin  in  its  physical  properties.  It 
is  extremely  susceptible  to  temperature  changes,  and  as  ordinarily 
produced,  is  hard  and  friable  at  77°  F.  It  is  characterized  by  the 
presence  of  considerable  quantities  of  unaltered  resin  acids  (10  to 
45  percent),  and  is  free  from  fatty  acids,  glycerol,  sulfur  and  paraf- 
fin. It  withstands  weathering  very  poorly,  and  has  therefore  but  a 
limited  use,  including  the  lining  of  barrels  and  casks  ("brewers' 
pitch") .  Upon  being  heated,  it  passes  rapidly  from  the  solid  to  the 
liquid  state,  forming  a  melt  of  low  viscosity.  A  product  similar  to 
rosin  pitch  may  be  produced  by  heating  rosin  with  sulfur  at  250°  C.24 
Burgundy  pitch"  is  the  name  applied  to  the  oleo-resin  which 
exudes  from  the  Norway  spruce  (Abies  excelsa},  found  in  the 
Vosges  Mountains  and  in  the  Alps;  also  from  a  species  of  pine  ob- 
tained in  the  United  States  (Pinus  australis).  The  crude  oleo-resin 
is  melted  by  boiling  with  water,  and  strained  to  remove  any  par- 
ticles of  bark  or  other  impurities.  It  then  constitutes  the  so-called 
"Burgundy  pitch"  (Fix  abietina],  sometimes  marketed  under  the 
name  "Vosges  pitch/'  These  terms  are  misnomers,  since  the  ma- 
terial is  not  a  true  "pitch,"  but  in  reality  an  oleo-resin.  It  contains 
more  or  less  spirits  of  turpentine,  which  escaped  expulsion  during 
the  boiling  process,  also  a  quantity  of  emulsified  water  imparting  to 
it  an  opaque,  yellowish-brown  color.  In  consistency  it  is  a  more  or 
less  brittle  solid,  largely  susceptible  to  temperature  changes.  In 
summer  it  softens  and  gradually  flows,  and  in  winter  it  appears  very 
hard  and  brittle.  It  melts  easily,  decrepitating  because  of  the  water 
present,  and  has  a  strong  odor  because  of  the  associated  spirits  of 
turpentine.  On  aging  it  loses  its  opacity,  due  to  evaporation  of  the 
emulsified  water,  and  turns  first  to  a  translucent,  and  then  to  a  trans- 
parent brown  color,  similar  to  that  of  rosin.  Its  composition  is 
substantially  the  same  as  rosin,  containing  in  addition,  spirits  of 
turpentine  and  emulsified  water. 


CHAPTER  XV 

PEAT  AND  LIGNITE  TARS  AND  PITCHES 

PEAT  TAR  AND  PEAT-TAR  PITCH 

Formation  of  Peat.  Peat *  is  derived  from  the  decomposition 
of  vegetable  matter  in  swampy  places,  such  as  marshes  and  bogs. 
On  the  surface  we  find  the  growing  aquatic  plants;  somewhat  deeper 
we  find  their  decayed  remains;  and  still  deeper  a  dark  colored  pasty 
substance  containing  a  substantial  percentage  of  moisture  and  con- 
stituting the  crude  peat.  The  plants  which  result  in  the  formation 
of  these  deposits  are  mainly  aquatic,  including  marine  grasses,  reeds, 
rushes,  hedges  and  various  mosses.  The  transformation  is  caused 
partly  by  oxidation  in  the  presence  of  moisture,  and  also  to  some 
extent  by  the  action  of  certain  forms  of  bacteria,  molds  and  fungi. 
As  the  mass  of  peat  builds  up  in  thickness,  the  lower  layers  are  first 
compacted  by  the  resulting  pressure,  and  then  gradually  carbonized. 
The  essential  condition  to  peat  formation  is  that  the  vegetable  re- 
mains shall  be  deposited  at  a  rate  exceeding  that  of  their  decompo- 
sition. This  does  not  prove  to  be  the  case  in  very  warm  climates, 
where  the  remains  are  entirely  decomposed.  The  organic  matter 
should  only  be  partly  decomposed,  and  since  the  products  of  partial 
decomposition  act  as  a  preservative  to  inhibit  further  decay,  we  can 
readily  understand  why  the  building  up  of  peat  beds  is  cumulative. 
It  progresses  most  rapidly  at  a  mean  atmospheric  temperature  of 
45°  FM  which  accounts  for  the  fact  that  no  peat  bogs  occur  between 
the  latitudes  of  45°  N.,  and  45°  S.  It  is  estimated  that  there  exist 
in  the  United  States  20  million  acres  of  peat  bogs,  30  million  acres 
in  Canada,  50  million  on  the  continent  of  Europe,  also  approxi- 
mately 3  million  in  Ireland. 

Varieties  of  Peat.  The  following  constitute  the  most  important 
varieties  of  peat,  based  on  the  locality  in  which  they  are  found : 

(i)  "Hill  peat,n  found  at  mountain  tops  and  derived  from 
plants  consisting  of  sphagnum  and  andromeda  mosses,  likewise 
heath, 

305 


306  PEAT  AND  LIGNITE  TARS  AND  PITCHES  XV 

(2)  "Bottom  peat,"  found  near  rivers,  lakes,  etc.,  in  the  low- 
lands, including:  (a)  dark  peat,  approaching  lignite  in  composition, 
occurring  at  the  lower  parts  of  the  deposit;  (b)  middle  peat,  which 
is  lighter  in  color  and  in  weight  than  the  preceding;  (c)  the  top 
stratum,  which  has  a  fibrous  structure. 

Peat  varies  in  color  from  light  yellowish,  through  various  tints 
of  brown,  to  brownish  black  or  black,  all  of  which  appear  deeper 
when  the  peat  is  moist  The  lighter  shades  generally  darken  to 
brownish  black  or  black  upon  exposure  to  air ;  due  largely  to  oxida- 
tion* In  texture,  peat  varies  from  light  porous  matter  having  a 
fibrous  or  woody  structure,  to  substances  which  are  amorphous  and 
clay-like  when  wet,  but  appearing  quite  hard  and  dense  upon  drying. 
When  recently  formed,  the  peat  beds  are  but  loosely  compacted,  but 
as  they  accumulate,  the  under  layers  become  compressed,  so  what 
once  was  a  foot  thick  may  be  concentrated  to  several  inches.  In 
other  cases  the  beds  become  covered  with  sedimentary  rocks,  which 
augment  the  pressure,  and  gradually  transform  the  peat  into  lignite. 

The  chemical  composition  of  peat  is  but  little  understood.  It  is 
regarded  as  a  mixture  of  water,  inorganic  matter  (calcium  and  iron 
compounds),  vegetable  fibers  and  humus  acids  (such  as  humic, 
ulmic,  crenic,  apocrenic,  etc.).  According  to  H.  Borntrager  2  the 
black  varieties  contain  between  25  and  60  per  cent  of  humic  acids, 
30  to  60  per  cent  of  fiber,  and  3  to  5  per  cent  of  ash.  Nitrogenous 
compounds  are  also  present,  varying  from  I  to  3  per  cent  of  the 
dry  weight,  resulting  partly  from  the  associated  animal  matter,  and 
also  due  partly  to  the  humic  acids  combining  with  atmospheric  nitro- 
gen, forming  what  are  known  as  azo-humic  acids.  Sulfur  is  also 
present  in  amounts  between  o.i  and  5,3  per  cent  based  on  the  dry 
weight. 

Resinous  substances  are  found  in  certain  varieties  of  peat,  to 
which  various  names  have  been  assigned,  also  bodies  of  a  waxy 
nature  derived  from  the  associated  gelatinous  algae,  known  as 
"sapropel."  In  time,  sapropel  is  converted  into  a  coal-like  sub- 
stance, known  as  sapropelite,  or  sapropelite  coal,  which  has  been 
regarded  as  the  progenitor  of  cannel  coal  and  boghead  coal. 

Methods  of  Collecting  Peat.  Peat  is  generally  collected  by 
cutting  trenches  through  the  bog  with  a  spade,  and  removing  it  in 
sods  about  3  to  4  ft.  long.  The  deposits  are  worked  in  steps  or 


XV  PEAT  TAR  AND  PEAT-TAR  PITCH  307 

tiers.  Mechanical  excavators  and  dredges  have  also  been  used  for 
the  purpose.  The  sods  are  allowed  to  drain,  then  air-dried  and 
finally  heated  to  a  high  temperature  in  either  stationary  or  revolv- 
ing ovens,  to  remove  the  water.  Peat  as  freshly  mined  contains  75 
and  90  per  cent  by  weight  of  water,  which  must  of  necessity  be 
removed  before  the  product  can  be  used  as  a  fuel.  Air-dried  peat 
carries  10  to  15  per  cent  of  moisture,  and  the  artificially  dried 
peat  between  a  trace  and  80  per  cent  of  mineral  ash,  consisting 
principally  of  sand  and  clay  with  smaller  quantities  of  iron  oxide, 
calcium  and  magnesium  salts.  The  maximum  quantity  of  ash  usually 
considered  allowable  when  used  as  a  fuel  is  25  per  cent  of  the  dry 
weight.  Peat  with  less  than  5  per  cent  ash  is  considered  good,  be- 
tween 5  and  10  per  cent  as  fair,  and  over  10  per  cent  as  poor, 
with  peat  containing  less  than  10  per  cent  of  ash  in  the  moisture- 
free  state,  the  fixed  carbon  varies  between  15  and  35  per  cent, 
averaging  about  30  per  cent. 

Dehydrating  Processes.  It  is  customary  to  briquette  the  partly 
dried  peat,  carrying  10  to  15  per  cent  of  water,  and  then  continu- 
ing the  drying  until  practically  all  the  moisture  is  removed,  and  the 
residual  peat  compacted  into  tough  briquettes  suitable  for  use  as 
fuel.  It  is  briquetted  under  a  pressure  of  18,000  to  30,000  Ib.  per 
square  inch,  which  generates  sufficient  heat  to  liberate  some  of  the 
tarry  compounds  of  the  peat,  causing  the  sides  of  the  briquettes  to 
assume  a  highly  polished  glaze.  The  product  is  claimed  to  have 
a  calorific  value  almost  equal  to  that  of  coal.  Various  mechanical 
contrivances  have  been  devised  for  removing  the  water  and  mois- 
ture from  peat. 

In  Europe  and  Canada,  attempts  have  been  made  to  utilize  air- 
dried  peat  for  generating  producer  gas.  Various  types  of  apparatus 
have  been  devised  for  the  purpose,  which  result  in  the  recovery  of 
i  to  2  per  cent  of  peat  tar,  based  on  the  dry  weight  of  the  peat8 
In  generators  (e.g.,  Mond  gas  generators)  from '8  to  9  per  cent  of 
tar  is  recovered,  and  in  low  temperature  distillation  processes  from 
8  to  25  per  cent  is  recovered. 

Methods  of  Distilling.  Various  methods  have  been  used  for 
distilling  peat,  similar  to  those  employed  for  treating  coal.  Dried 
peat  may  be  destructively  distilled  in  closed  retorts,  obtaining  a  gas 
suitable  for  use  as  a  fuel,  likewise  tar,  ammonia,  and  a  good  grade 


308  ,  PEAT  AND  UGNITE  TARS  AND  PITCHES  XV 

of  coke,  but  in  the  United  States  this  process  has  only  been  carried 
on  in  a  small  experimental  way.  There  are  two  classes  of  peat  tar, 
lamely  retort  peat  tar  and  producer  peat  tar,  both  of  which  are 
low-temperature  products  generated  at  not  exceeding  600°  C  At 
the  present  time  the  cost  of  drying  and  briquetting  peat  brings  its 
price  higher  than  that  of  bituminous  coal.  For  these  reasons  neither 
peat  tar  nor  peat-tar  pitch  are  produced  in  commercial  quantities. 
The  following  represent  the  percentages  by  weight  of  by-prod- 
ucts obtained  per  ton  of  the  air-dried  peat: 

Gases  and  loss Ia-ao  per  cent 

Aqueous  liquor 30-40  per  Cent 

Peat  tar 2-10  per  cent 

Coke 30-40  per  cent 

100    per  cent 

The  composition  of  an  average  specimen  of  peat  tar  is  as 
follows : 

Insoluble  in  ether  (i.e.,  oxy-acids  and  their  esters,  also  iron  and  cal- 
cium derivatives)  3  per  cent 

Soluble  in  ether: 


•  • 5  per  cent 

Unsaponifiable  substances: 

Solid  portion 8  per  cent 

Liquid  portion 55  pcr  cent 

Saponifiabie  substances: 
Oxy-^cids — 

Insoluble  in  ether 3  per  cent 

Soluble  in  ether 8  per  cent 

Fatty  acids 10  per  cent 

Phenols , 3i  per  cent 

4i  per  cent 

Total 100  per  cent 

The  following  yields  are  obtained  from  German  peat: 

Water-free  peat  tar 4, 9  to  9,9  per  cent 

Light  oils  (sp.  gr,  o. 820-0. 835) 7-3  to  34. 6  per  cent 

Heavy  oils  (sp.  gr,  0.830-0.885) 19.6  to  36.0  per  cent 

Paraffin '. 3.3  to  46.0  per  cent 

Peat-tar  pitch 12.8  to  w. 6  per  cent 

Creosote  oil  and  loss 6.2  to  40.5  percent 

Refining  Processes.  The  tar  is  separated  from  the  aqueous 
liquor  by  heating  the  mixture  with  steam  to  the  melting-point  of  the 
tar,  which  then  rises  to  the  surface.  It  is  a  black,  viscid  liquid 
with  a  disagreeable  acrid  odor,  representing  a  to  20  per  cent  of 


XV 


PEAT  TAR  AND  PEAT-TAR  PITCH 


309 


the  dry  weight  of  the  peat  used.  The  aqueous  liquor  contains  am- 
monia salts,  acetic  and  other  organic  acids,  wood  alcohol,  and  pyri- 
dine  bases.  The  tar  is  slowly  distilled,  and  after  the  water  ceases 
to  pass  over,  the  receiver  is  changed  and  the  distillation  continued 
until  45  per  cent  of  oily  distillate  has  been  collected.  The  receiver 
is  again  changed,  and  heavy  oils  containing  paraffin  wax,  totalling 
about  30  per  cent  by  weight  of  the  tar,  are  caught  separately, 
leaving  15  to  20  per  cent  of  peat-tar  pitch  in  the  retort,  which  is 
finally  drawn  off.  The  oily  distillate  first  obtained  is  redistilled 
into  light  naphtha  (density  under  0.83),  and  heavy  naphtha  (den- 
sity 0.85).  The  heavy  oil  is  cooled  and  pressed  to  separate  lubri- 
cating oil  from  the  paraffin  wax.  The  products  are  treated  first 
with  concentrated  sulfuric  acid  and  then  with  caustic  soda  to  re- 
move tarry  impurities  and  creosote  oil  respectively,  the  latter  being 
recovered  in  the  form  of  creosote  or  carbolic  acid. 
The  dry  peat  tar  yields  the  following : 


Crude, 
Per  Cent 

After  Purification, 
Per  Cent 

Light  naphtha  

16 

11 

Heavy  naphtha  

1Q 

1C 

Lubricating  oil  

o^ 
1C 

^j 

1  O 

Paraffin  wax  

1  j 
12 

X3 

« 

Peat-tar  pitch  

16 

16 

Creosote  

frt 

Loss  

1  1 

on 

100 

100 

A  diagrammatical  outline  of  the  various  products  obtained  on 
the  dry-distillation  of  peat  is  given  in  Table  XX. 


TABLE  XX 

PEAT 

(Dry  distilled) 

• 

Gas  (57%) 

Aqueous  liquor  (46%) 
Distilled: 

Peat  tar  (4%) 
Distilled: 

1 

Coke  (ag%) 

1                     i 
Wood         Ammonia 
alcohol       (o.i6%> 
(0,34%) 

i           i             i 

Acetic        Losses  and           Light 
acid            water                  oil 
(0.44%)                                   (»%) 

1                I 
Heavy      Paraffin 
oU         (0.3%) 

1                 1 
Phen-          Pitch 
olatc         (0.2%) 

310  PEAT  AND  LIGNITE  TARS  AND  PITCHES  XV 

Properties  of  Peat  Tar.     Dehydrated  peat  tars  in  general,  test 
as  follows: 

(Test    i)     Color  in  mass Black 

(Test   7)    Specific  gravity  at  77°  F 0.90-1 .05 

(Test    9)    Hardness  or  consistency Liquid 

(Test  i  fa)  Fusing-point  (K.  and  S.  method) 40-60°  F. 

(Test  16)    Volatile  matter  at  500°  F.,  in  5  hrs 50-85  per  cent 

(Test  17*)  Flash-point 60-95°  F. 

(Test  19)     Fixed  carbon 5-15  per  cent 

(Test  at)     Soluble  in  carbon  disulfide 98-100  per  cent 

Non-mineral  matter  insoluble o-    2  per  cent 

Mineral  matter o-     i  per  cent 

(Test  22)    Carbenes o-    2  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha 95-100  per  cent 

(Test  28)    Sulfur Less  than  i  per  cent 

(Test  30)    Oxygen  in  non-mineral  matter 5-15  per  cent 

(Test  33)    Solid  paraffins 5-15  per  cent 

(Test  34^)  Sulfonation  residue 5-15  per  cent 

(Test  37*)  Saponifiable  constituents 5-15  per  cent 

(Test  39)     Diazo  reaction Yes 

(Test  40)    Anthraquinone  reaction No 

(Test  41)    Liebermann-S  torch  reaction No 

Properties  of  Peat-tar  Pitch.  Peat-tar  pitch  is  obtained  by  the 
evaporation  or  steam  distillation  of  peat  tar.  It  is  not  an  article 
of  commerce  in  the  United  States.  Its  hardness  or  consistency, 
as  well  as  its  f  using-point,  depend  upon  the  extent  to  which  the  dis- 
tillation has  been  conducted.  Ordinarily,  peat-tar  pitch  tests  much 
the  same  as  lignite-tar  pitch,  the  results  being  included  in  Table 
LXXXIV.  It  is  highly  susceptible  to  temperature  changes,  and 
withstands  exposure  to  the  weather  very  poorly. 


LIGNITE  TAR  AND  LIGNITE-TAR  PITCH  * 

Varieties  of  Lignite.  The  U.  S.  Geological  Survey  estimates 
that  1,087,514,400,000  tons  of  lignite  are  available  in  the  United 
States,  but  it  is  used  only  in  a  limited  way,  due  to  the  abundance 
of  other  types  of  fuel.  Large  deposits  occur  also  in  Alberta,  Sas- 
katchewan and  Manitoba,  Canada.  A  zone  covering  about  1700 
square  miles  has  been  located  in  Australia,  and  one  small  deposit 
has  been  reported  in  England  (at  Bovey-Tracey  in  Devonshire). 
In  Germany,  however,  the  lignite  industry  has  made  much  more 
rapid  advances,  owing  partly  to  the  scarcity  of  high-grade  coals,  and 
partly  to  the  fact  that  the  deposits  are  located  close  to  large  cities, 


XV  LIGNITE  TAR  AND  UGN1TE-TAR  PITCH  311 

making  the  cost  of  transportation  low.    The  lignite  is  accordingly 
used  as  a  fuel  for  steam  plantsf  for  manufacturing  producer  gas, 
and  for  distillation  purposes  to  recover  its  valuable  by-products. 
The  descriptions  of  the  methods  which  follow  are  based  on 

German  practice  as  carried  out  in  the  following  localities,  viz. : 

? 

1 i )  Near  Horrem,  a  short  distance  west  of  Cologne  in  Rhine  Prov- 

ince; 

(2)  In  the  neighborhood  of  Halle  on  the  Saale,  in  the  Proyinces 

of  Saxony  and  Thuringia;  and 

(3)  At  Messel,  near  Darmstadt  in  Hessen  Province. 

The  so-called  browncoal  (variety  of  lignite)  is  mined  at  the  first 
two  localities.  It  is  estimated  that  20,000  to  25,000  tons  are  bri- 
quetted  daily  in  the  Cologne  mining  district  alone,  where  the  beds 
run  from  30  to  350  ft.  thick,  averaging  75  ft;  Browncoal  differs 
somewhat  from  American  lignite  in  carrying  a  higher  percentage 
of  moisture  (about  60  per  cent  instead  of  25  to  50  per  cent). 
American  lignites  generally  resemble  bituminous  coal  in  hardness 
and  appearance,  whereas  browncoal  is  distinctly  earthy  in  appearance 
and  is  soft  and  friable  enough  to  be  dug  with  a  spade.  Moreover, 
browncoal  contains  up  to  13  per  cent  waxy  constituents  which  are 
of  great  value  as  a  binder  in  briquetting,  whereas  American  lignites 
contain  less  than  1.5  per  cent  of  binder,  and  are  unsuitable  for 
briquetting  when  used  alone.  As  mined,  browncoal  is  soft  and  either 
unconsolidated  or  but  slightly  consolidated.  The  Messel  deposit 
carries  about  30  per  cent  clay  and  45  per  cent  water,  the  organic 
constituents  apparently  being  combined  chemically  with  the  clay. 
It  is  greasy  in  consistency,  having  a  black  color  with  a  greenish  cast. 
The  bed  covers  about  240  acres  in  hemispherical  depression,  and 
measures  480  ft.  in  thickness,  under  a  cover  13  ft.  thick  composed 
of  gravel  and  clay. 

Mining  Methods.  Browncoal  in  the  Cologne  and  Halle  re- 
gions is  found  in  stratified  beds  in  which  the  layers  alternately  ap- 
pear lighter  and  darker  in  color.  The  lighter  layers  form  a 
brownish-black  plastic  and  greasy  mass  when  freshly  mined,  and  a 
yellowish  to  light  brown  pulverulent  substance  when  dry.  They  are 
characterized  by  the  presence  of  waxy  constituents  (soluble  in  car- 
bon disuifide,  benzol,  etc.)  The  darker  layers  form  a  black  plastic 


312  PEAT  AND  LIGNITE  TA&S  AND  PITCHES  XV 

mass  when  fresh,  and  a  dark-brown  to  black  earthy  substance  after 
drying.  They  differ  from  the  light-colored  layers,  in  being  sub- 
stantially free  from  waxy  constituents.  The  two  varieties  are 
sorted  during  the  process  of  mining.  The  light-colored  product 
resembles  the  mineral  pyropissite. 

The  lighted  variety  of  lignite  has  been  incorrectly  termed 
"bituminous  lignite,"  and  the  darker,  "non-bituminous  lignite."  For 
purposes  of  differentiation,  we  will  refer  to  them  as  "retort  lignite" 
and  "fuel  lignite"  respectively.*  Retort  lignite  ranges  in  specific 
gravity  from  0.9  to  i.i  and  melts  at  ignition,  whereas  fuel  lignite 
has  a  gravity  of  1.2  to  1.4,  and  does  not  melt, 

It  is  assumed  that  these  two  varieties  of  lignite,  since  they  occur 
in  the  same  deposit,  result  from  differing  conditions  surrounding 
their  formation,  as  for  example  a  variation  in  water  level.  Thus 
if  the  original  vegetable  matter  containing  a  large  amount  of  waxy 
constituents  was  protected  from  the  action  of  atmospheric  oxygen 
by  being  surrounded  with  vfater  until  the  transformation  into  lignite 
had  been  completed,  then  the  woody  tissue  was  more  or  less  pre- 
served, and  fuel  lignite  resulted.  If,  however,  the  water  receded 
and  exposed  the  deposit  to  the  action  of  air,  then  the  woody  tissue 
became  partly  or  wholly  oxidized,  leaving  the  more  resistant  ma- 
terials behind,  and  resulting  in  the  formation  of  retort  lignite.  If  the 
process  of  atmospheric  oxidation  had  been  carried  to  the  greatest 
pdssible  extent,  then  the  waxes  only  remain  behind,  in  the  form  of 
the  mineral  pyropissite,  which,  however,  is  no  longer  mined,  since  its 
total  available  supply  has  been  exhausted.  Lignite  as  freshly  mined 
is  more  or  less  rapidly  acted  upon  by  atmospheric  oxygen,  the  dark 
variety  being  more  susceptible  than  the  light  one.  A  typical  lignite 
vein  carries  about  twice  as  much  fuel  lignite  as  retort  lignite. 

Lignite  is  mined  by  the  open-cut  method  where  the  over-burden 
is  not  very  thick,  or  by  driving  shafts  and  tunnels  when  the  bed  is 
situated  sortie  distance  below  the  surface.  In  the  case  of  open-cut 
mJfiirig,  the  overburden  is  first  removed  with  steam  shovels,  and  the 
ligijite  excavated  by  mechanically  operated  chain  and  buckets,  which 
load  the  material  into  small  skips. 

•la  Gerpany  they  are  termed  "Distillation  Coal1'  (SchwelkoUe)  and  "Fire  Coal" 


XV  LIGNITE  TAR  AND  LIGNITE-TAR  PITCH  313 

Shaft  mining  presents  a  number  of  difficulties  owing  to  the  soft- 
ness and  unstability  of  the  crude  lignite.  The  shafts  must  be  well 
timbered,  and  in  many  cases  it  is  first  necessary  to  freeze  the  lignite 
before  it  can  be  handled. 

Methods  of  Distilling.  Retort  lignite  is  treated  in  one  of  two 
ways,  viz. : 

(1)  It  is  subjected  directly  to  low-temperature  destructive  dis- 
tillation 6  or 

(2)  It  is  first  extracted  with  a  solvent  to  remove  the  montan 
wax  and  the  residue  either  distilled  destructively  or  briquetted  and 
sold  as  fuel. 

Fuel  lignite  is  also  treated  in  one  of  two  ways,  viz. : 

(1)  If  it  is  comparatively  free  from  ash,  it  is  briquetted  and 
used  as  fuel ;  or 

(2)  If  it  contains  a  large  proportion  of  ash,  as  with  Messel 
lignite,  it  is  used  for  manufacturing  producer  gas  by  combustion  in 
an  atmosphere  of  air  and  steam,  so  that  practically  all  the  carbon- 
aceous matter  is  consumed,  leaving  almost  pure  ash  behind.    Smce 
Messel  lignite  in  its  crude  state  contains  but  25  per  cent  of  com- 
bustible material,  it  is  unsuitable  for  use  as  fuel,  or  for  purposes 
of  destructive  distillation. 


When  the  lignite  is  to  be  used  for  fuel,  it  is  converted  into 
briquettes  by  subjecting  the  granulated  material  to  great  pressure. 
The  heat  generated  during  this  operation  softens  the  waxy  sub- 
stances present,  and  binds  the  particles  into  a  solid  mass.  It  is 
unnecessary,  therefore,  to  add  any  extraneous  binding  medium. 

In  manufacturing  briquettes,  the  lignite  is  first  crushed  to  about 
the  size  of  peas,  then  passed  through  a  drier  to  reduce  the  moisture 
to  approximately  15  per  cent.  A  tubular  drier,  heated  with  steam, 
has  been  found  most  satisfactory  for  the  purpose.6  The  lignite 
powder  is  fed  into  a  briquetting  press,  where  it  is  subjected  to  a 
pressure  between  18,000  and  22,500  Ib.  per  square  inch. 

Retort  lignite  is  unsuitable  for  fuel  or  manufacturing  briquettes, 
as  the  large  quantity  of  waxy  constituents  present  will  soften  when 
heated,  causing  the  briquettes  to  melt  and  drop  through  the  grate 


314 


PEAT  AND  LIGNITE  TARS  AND  PITCHES 


XV 


bars.  When  the  retort  lignite  has  been  extracted  with  solvents  to 
remove  the  "montan  wax/'  the  residue  retains  enough  waxy  con- 
stituents to  enable  it  to  be  briquetted. 

When  the  retort  lignite  is  to  be  subjected  to  destructive  distilla- 
tion, it  is  used  directly  as 
it  comes  from  the  mine, 
without  drying.  In  fact, 
the  presence  of  the  water 
materially  assists  the  dis- 
tillation process  by  pre- 
venting the  volatile  prod- 
ucts from  decomposing 
too  extensively.  The 
water  is  converted  into 
steam  which  quickly  re- 
moves the  vapors  from 
the  hot  retort  and  pre- 
vents cracking,  thus  in- 
creasing the  yield  of  tar. 
Taking  the  yield  of  tar 
from  freshly  mined  lignite 
as  loo,  the  yield  from  air- 
dried  lignite  is  about  74, 
and  from  lignite  dried  at 
105°  C.  approximately  56-. 
Practice  has  shown 
that  the  moisture  content 
should  not  be  less  than  30 
per  cent.  In  distilling  lig- 
nite, the  humic  acids  pres- 
ent are  converted  into  the 

so-called  "neutral  bodies,"  the  cellulose  derivatives  into  phenolic 
bodies  and  unsaturated  hydrocarbons,  and  the  waxy  constituents  into 
saturated  hydrocarbons  and  paraffin  wax. 

It  is  claimed  that  the  Rolle  retort  shown  diagrammatically  in 
Fig,  96  has  been  found  most  satisfactory  for  treating  3-5  tons  lignite 
per  day.  It  is  5  to  6  ft*  in  diameter  by  20  to  25  ft.  high,  and  works 
continuously,  the  operation  progressing  in  two  stages,  viz.: 


FIG.  96. — Retort  for  Distilling  Lignite. 


XV  LIGNITE  TAR  AND  UGNITE-TAR  PITCH  315 

1 i )  Drying  the  lignite. 

(2)  Decomposing  the  lignite  into  gas,  water,  tar  and  coke. 

The  contrivance  is  composed  essentially  of  two  concentric  cylin- 
ders, an  outer  one  of  fire  brick  and  an  inner  one  consisting  of  a  stack 
of  conical  rings  assembled  in  louvre  fashion,  constructed  of  iron  or 
fire  clay.  The  lignite  after  being  crushed  into  lumps  about  il/2,  to 
2l/2  in.  in  diameter  is  introduced  into  the  space  between  the  con- 
centric cylinders.  The  products  of  distillation  pass  out  through  the 
flues  A  and  B.  The  openings  C  represent  the  fire-flues;  D;  the 
stack  of  conical  rings;  E,  the  cap  covering  the  rings;  F,  an  inverted 
cone  of  metal  into  which  the  coke  falls  after  the  lignite  has  been 
thoroughly  carbonized;  G,  a  device  for  intermittently  drawing  off 
the  coke ;  H,  the  combustion  chamber ;  /,  vents  for  introducing  the 
gases;  Ky  the  pipes  through  which  the  gases  enter;  and  L,  the  fire 
place  which  comes  into  play  when  the  retort  is  first  started  up.  Coal 
or  lignite  is  burnt  on  the  grate,  until  the  process  of  destructive  dis- 
tillation commences,  whereupon  the  resulting  non-condensable  gases 
are  introduced  through  K  and  /,  and  caused  to  burn  in  the  flues  C. 
The  space  over  the  cap  E  is  kept  filled  with  lignite,  and  the  rate  of 
travel  through  the  retort  is  controlled  by  the  frequency  with  which 
the  coke  is  removed  from  the  chamber  G. 

The  temperature  at  which  the  distillation  takes  place  varies 
between  500  and  900°  F.,  and  the  vapors  issue  from  the  retort  at 
250  to  300°  F.  The  products  of  decomposition  are  drawn  from  the 
retort  by  a  slight  suction,  and  passed  through  a  series  of  air  con- 
densers, which  removes  most  of  the  tar,  the  high  boiling-point  oils, 
and  part  of  the  water.  The  condensation  is  completed  by  passing 
the  gases  through  pipes  surrounded  by  water. 

The  tar  is  separated  from  the  condensed  water  by  warming  it 
and  allowing  it  to  stand  quietly  in  a  suitable  receptacle.  The  tar 
being  lighter  than  the  water,  rises  to  the  surface,  and  is  drawn  off 
when  the  separation  is  complete. 

Products  Obtained.  A  bituminous  lignite  containing  20-30  per 
cent  moisture  and  15-16  per  cent  soluble  in  carbon  disulfide, 
yielded  24  per  cent  tar  having  a  specific  gravity  of  0.885  at  50°  C., 
a  solidifying  point  of  37°  C.,  and  containing  16  per  cent  creosote 
oils.  Similarly,  a  non-bituminous  lignite  containing  15  per  cent 


316 


PEAT  AND  LIGNITE  TARS  AND  PITCHES 


XV 


moisture  and  3-4  per  cent  soluble  in  carbon  disulfide,  yielded  7.6 
per  cent  tar  having  a  specific  gravity  of  0.955  at  5°°  C.,  a  solidi- 
fying point  33°  C,  and  containing  37  per  cent  creosote  oils.  On 
fractional  distillation  with  superheated  steam,  the  former  yielded 
3.2  per  cent  pitch  and  the  latter  8.5  per  cent 
The  following  yields  are  obtained : 

Lignite  tar  (vertical  retorts) up  to  7  per  cent 

"       "  (low  temperature) 7  to  12  per  cent 

Brown-coal  tar  (Rolle  retort) 4  to  8  per  cent 

"       "      "   (low-temperature) 8  to  24  per  cent 

A  commercial  product  known  as  "kaumazite"  is  made  from 
Bohemian  lignite  by  a  process  of  low-temperature  distillation. 

In  recent  years  the  following 
products  have  been  recovered : 

Water 50-60  per  cent 

Tar 5-10  per  cent 

Coke 25-35  per  cent 

Gas Balance 

Treating  Impure  Lignite.  The 
Messel  lignite  carrying  a  large  per- 
centage of  mineral  matter  is  treated 
in  a  special  form  of  retort  built  in 
batteries,  as  illustrated  in  Fig,  97, 
The  process  takes  place  in  three 
stages,  viz.  : 

1 i )  Drying  of  the  lignite  and  ac- 
companying generation  of  steam,  tak- 
ing place  in  the  zones  c. 

(2)  Distillation  of  the  dried  ma- 
terial, taking  place  in  zones  b. 

(3)  Combustion  of  the  residual 
coke  by  means  of  air  and  the  steam 
generated   in    (i),    taking  place  in 
zones    a.     The   steam   liberated    in 
zones  c  is  passed  through  the  flues 
G-tf,  /-/,  and  G-^;  respectively,  into 
zones  aj  as  illustrated. 


Fie.  97.— Retort  for  Distilling 
Impure  Lignite. 


In  other  words,  the  steam  generated  by  the  lignite  itself,  is  used 
to  decompose  the  coke  into  producer  gas,    The  gas  is  caused  to  burn 


XV  LIGNITE  TAR  AND  LIGNITE-TAR  PITCH  317 

in  the  chambers  A,  B  and  C  respectively,  the  products  of  combus- 
tion passing  through  the  openings  o)  o.  Pipe  d  represents  the  out- 
let for  the  products  of  decomposition,  and  s  represents  the  supply 
pipe  for  the  heated  gas.  The  paths  of  the  products  are  indicated  by 
the  arrows.  The  yield  of  tar  varies  between  4  and  14  per  cent, 
averaging  about  ^l/2  per  cent  (19  gallons  per  ton),  that  of  gas  6 
per  cent,  water  44  per  cent  and  coke  36  per  cent.  The  residue  dis- 
charged from  the  bottom  of  the  retort  is  composed  of  mineral  mat- 
ter carrying  8  per  cent  of  undecomposed  carbon.  More  gas  is  gen- 
erated during  the  process  than  is  required  for  heating  the  retort, 
hence  the  excess  is  used  for  other  purposes. 

Lignite  in  either  the  air-dried  or  briquetted  form  is  gradually 
being  used  more  and  more,  especially  in  Europe,  for  manufacturing 
producer  gas.  About  60  cu.  ft.  of  gas  are  produced  from  each 
pound  of  the  dry  lignite,  also  l/±  to  l/2  per  cent  by  weight  of  lignite 
tar,  which  is  separated  from  the  producer  gas  in  the  usual  manner. 

In  certain  localities  (e.  g.  northern  Bohemia)  lignite  is  carbon- 
ized in  a  variety  of  coke-oven,  similar  to  that  used  for  treating 
coal,  to  produce  coke,  during  which  process  a  tar  is  obtained  known 
as  coke-oven  lignite-tar.  The  carbonization  takes  place  at  1100°  C. 
and  the  resulting  tar  has  a  specific  gravity  at  60°  C.  of  0.970. 

Properties  of  Lignite  Tar.  Lignite  tar  has  a  buttery  consist- 
ency at  ordinary  temperatures  and  a  dark  brown  to  black  color.  It 
is  composed  of  liquid  and  solid  members  of  the  paraffin  and  olefine 
series,  together  with  a  small  quantity  of  the  benzol  series,  also  the 
higher  phenols  and  their  derivatives  ( fo  to  25  per  cent) .  It  is  char- 
acterized by  the  presence  of  a  substantial  proportion  of  solid  paraf- 
fin (10  to  25  per  cent)  and  from  0.5  to  1.5  per  cent  of  sulfur. 

Four  different  varieties  of  lignite  tar  are  recognized,  viz. : 

(i)  Retort  tar  (e.  g.  from  Rolle  retorts). 

(2}  Low-temperature  lignite-tar   (produced  below  6po°  C.), 

)  Producer-gas  lignite-tar  (e.  g.  from  Messel  lignite). 

)  Coke-oven  lignite-tar  (e.  g.  northern  Bohemia). 

Lignite  tars  are  usually  emulsified  with  water,  which  separates 
with  difficulty,  and  when  derived  from  gas-producers  they  carry  a 
certain  amount  of  free  carbon  (up  to  3  per  cent).  Both  may  be 
removed  by  centrifuging.  Thus  a  tar  carrying  1 1.7  per  cent  water 
and  2.28  per  cent  free  carbon,  upon  centrifuging  at  4000  to  6000 


318  PEAT  AND  LIGNITE  TARS  AND  PITCHES  XV 

r,p.m.  at  60-85°  C.,  yielded  a  product  carrying  0.7  per  cent  water 
and  0.06  per  cent  free  carbon. 

In  general,  dehydrated  lignite  tar  conforms  with  the  following 
characteristics : 

(Test    i)     Color  in  mass Yellowish  brown  to 

greenish   brown  to 
brownish  black 

(Test    7)    Specific  gravity  at  77°  F o.  85-1 ,05 

(Test   9)    Hardness  or  consistency  at  77°  F Salve-like  to  buttery 

(Test  10)     Ductility  at  77°  F None 

(Test  150)  Fusing-point  (K.  and  S.  method) 60-90°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 75-100°  F. 

(Test  1 6)     Volatile  matter  at  500°  F.,  5  hrs 70-85  per  cent 

(Test  170)  Flash-point  (Pensky-Martens  tester) 7 5-90°  F. 

(Test  19)     Fixed  carbon 5-20  per  cent 

(Test  200)  Distillation  test The  boiling-point  ranges 

between  80  and  400° 
C.,  the  greater  por- 
tion distilling  between 
250  and  350°  C 

(Test  2i)     Soluble  in  carbon  disulphide 96-100  per  cent 

Non-mineral  matter  insoluble o-    a  per  cent 

Mineral  matter o-    i  per  cent 

(Test  22)    Carbenes o-    2  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha 98-100  per  cent 

(Test  28)     Sulfur o.  5-2 . 5  per  cent 

(Test  29)    Nitrogen Less  than  o.  i  per  cent 

(Test  30)    Oxygen 5-10  per  cent 

(Test  31)    Free  carbon o-i  per  cent 

(Test  32)    Naphthalene £-1  per  cent 

(Test  33)    Solid  paraffins 10-25  per  cent 

(Test  34^)  Sulfonation  residue 10-20  per  cent 

(Test  37*)  Saponifiable  constituents 5-20  per  cent 

(Test  39)    Diazo  reaction Yes 

(Test  40)    Anthraquinone  reaction No 

(Test  41)    Liebermann-S torch  reaction No 

Marcusson  and  Picard  7  have  reported  the  following  percent- 
ages of  saponifiable  constituents  present  in  normal  tar  from  Saxon- 
Thuringian  lignite :  saponifiable  constituents  7.4  per  cent,  consisting 
of  oxy-acids  soluble  in  ether  2.4  per  cent;  reported  as  fatty  acids 
3,0  per  cent;  and  phenols  2.0  per  cent  Generator  tar  from  Saxon- 
Thuringian  lignite:  saponifiable  constituents  14.0  per  cent,  com- 
posed of  oxy-acids  soluble  in  ether  0.5  per  cent;  oxy-acids  insoluble 
in  ether  4.0  per  cent;  reported  as  fatty  acids  4.5  per  cent;  and 
phenols  5.0  per  cent. 

Refining  Processes.  In  practice,  lignite  tar  is  distilled  to  sep- 
arate various  oils  and  paraffin  wax.  The  distillates  are  purified  by 


XV  LIGNITE  TAR  AND  LIGNITE-TAR  PITCH  319 

treatment  with  acids  and  alkali,  and  the  paraffin  by  re-crystalliz- 
ation. 

The  distillation  is  conducted  in  one  of  three  ways,  viz. : 


1 i )  At  atmospheric  pressure,  without  steam. 

(2 )  By  means  of  steam,  sometimes  after  treating  with  alkal 

(3)  Under  vacuum,  sometimes  supplemented  with  steam. 


Vacuum  distillation  is  generally  used,  as  it  saves  fuel,  reduces 
the  time  and  prevents  cracking  of  the  distillates.  The  best  prac- 
tice consists  in  using  a  slight  vacuum  at  the  beginning  of  the  distilla- 
tion, and  gradually  increasing  it  until  the  paraffin  begins  to  distil, 
when  it  is  maintained  at  1 6  to  28  in.  of  mercury  by  a  steam  injector, 
or  vacuum  pump. 

With  steam  distillation,  either  plain  or  superheated  steam  may 
be  used  and  direct  heating  of  the  retort  may  be  dispensed  with  in 
the  latter  case. 

The  distillation  may  be  intermittent  or  continuous.  European 
practice  provides  for  the  continuous  distillation  of  the  dehydrated 
tar  in  a  battery  of  vertical  cylindrical  stills  with  hemispherical  bot- 
toms, having  dome-shaped  tops.  Each  still  is  connected  with  a  con- 
denser composed  of  a  circular  coil  of  metal  piping  immersed  in  a 
water  tank.  Between  10  and  20  stills  are  erected  side  by  side  on  a 
common  brick  setting. 

Lignite  tar  is  first  distilled  to  %  its  original  bulk,  and  the  com- 
bined residues  of  several  stills  are  run  into  a  separate  retort.  In 
some  cases  the  residues  are  distilled  to  produce  lignite-tar  pitch,  but 
in  the  majority  they  are  distilled  until  nothing  but  coke  remains. 
By  thus  treating  the  residues  in  separate  retorts,  the  lives  of  the  first 
retorts  are  lengthened  materially,  and  the  wear  and  tear  concen- 
trated on  a  few.  The  retorts  in  which  the  preliminary  distillation 
takes  place  are  of  course  subjected  to  a  much  lower  temperature 
than  those  in  which  the  residues  are  treated. 

When  lignite  tar  is  distilled  to  coke,  a  certain  amount  of  crack- 
ing occurs  and  consequent  formation  of  tarry  matter  in  the  distill- 
ates, which  is  removed  by  treating  with  sulfuric  acid.  The  result- 
ing sludge  is  worked  up  into  lignite-tar  pitch  as  will  be  described 
later. 

Obviously  the  pitches  derived  in  these  two  ways  differ  in  their 


320  PEAT  AND  LIGNITE  TARS  AND  PITCHES  XV 

physical  properties,  and  particularly  in  the  quantity  of  associated 
paraffin,  which  is  smaller  in  lignite-tar-sludge  pitch. 

Products  Obtained.  The  tar  is  fractioned  into  crude  oil  (about 
33  per  cent),  a  paraffinaceous  distillate  (about  60  per  cent),  red 
oil  (about  3  per  cent),  and  yields  permanent  gases  (about  2  per 
cent),  and  coke  (about  2  per  cent). 

The  crude  oil  is  re-distilled  into  naphtha,  illuminating  oil,  clean- 
ing oil,  gas  oil  and  light  paraffin  oil  (vaseline  oil).  The  paraffin- 
aceous mass  is  cooled  and  pressed,  which  removes  the  heavy  paraf- 
fin oil  from  the  paraffin  wax.  The  paraffin  wax  is  then  re-crystal- 
lized and  separated  into  the  soft  paraffin  wax  and  hard  paraffin 
wax  respectively. 

According  to  Waldemar  Scheithauer,  an  average  grade  of  lig- 
nite tar  will  yield  the  following  products,  viz. :  benzine  5  per  cent, 
lubricating  oil  5  to  10  per  cent,  light  paraffin*  oils  10  per  cent, 
heavy  paraffin  oils  30  to  50  per  cent,  hard  paraffin  10  to  15  per  cent, 
soft  paraffin  3  to  6  per  cent,  dark-colored  products  3  to  5  per  cent/ 
coke,  gas  and  water  20  to  30  per  cent.  If  the  distillation  of  lignite 
tar  is  not  continued  to  coke,  lignite-tar  pitch  is  obtained,  amounting 
to  about  5  per  cent  by  weight  of  the  tar. 

The  diagram  in  Table  XXI  shows  the  essential  steps  in  treating 
lignite  tar  by  fractional  distillation,  including  the  two  alternatives  of 
running  to  pitch  and  coke  respectively. 

The  fractions  are  purified  by  treating  successively  with  weak  and 
strong  sulfuric  acid,  followed  by  caustic  soda,  which  improve  the 
color  and  odor,  and  enable  the  products  to  command  a  higher  price. 
The  preliminary  treatment  with  weak  sulfuric  acid  removes  a  por- 
tion of  the  basic  constituents,  including  the  pyridirie.  The  stronger 
sulfuric  acid  extracts  the  remaining  basic  substances,  the  tarry  mat- 
ters which  impart  a  dark  color,  a  portion  of  the  unsaturated  hydro- 
carbons and  the  resinous  constituents.  The  alkali  serves  to  neu- 
tralize the  acid,  and  to  remove  the  creosote  oils  which  would  impart 
a  disagreeable  odor  and  darken  on  exposure  to  light 

After  the  chemical  treatment,  the  acid  and  soda  sludges  are 
settled  off.  The  acid  sludge  is  boiled  with  steam  in  lead-lined  ves- 
sels, which  decomposes  it  into  pitch  and  sulfuric  acid  (30  to  40° 
Baume).  This  acid  is  used  for  decomposing  the  soda  sludge  into 
creosote  oil  and  sodium  sulfate  (Glauber  salt).  The  impure  creo- 


XV 


LIGNITE  TAR  AND  LIGNITE-TAR  PITCH 


321 


9 

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322  PEAT  AND  LIGNITE  TARS  AND  PITCHES  XV 

sote  containing  tarry  matters  is  mixed  with  the  pitch  separated  from 
the  acid  sludge,  and  after  washing  with  water  to  remove  all  traces 
of  acid  and  alkali,  the  mixture  is  distilled  with  superheated  steam. 
The  purified  lignite  creosote  is  recovered  as  distillate  (having  a 
specific  gravity  of  0.940  to  0,980,  and  yielding  50  to  70  per  cent 
soluble  in  caustic  soda)  and  the  lignite-tar  pitch  remains  as  residue. 
The  extent  to  which  the  distillation  is  continued  regulates  the  hard- 
ness and  fusing-point  of  the  pitch,  which  is  much  harder  in  consist- 
ency than  that  obtained  from  the  direct  distillation  of  lignite  tar. 
A  black,  glossy  pitch  of  good  quality  may  be  produced  by  treating 
lignite  tar  with  4  per  cent  sulfuric  acid  (60°  Baume)  at  160°  C. 
and  the  lower  pitch-like  layer  heated  with  20  per  cent  anthracene 
oil  at  250°  C.9 

Properties  of  Lignite-tar  Pitch.     Lignite-tar  pitches  conform 
with  the  following  tests : 

(Test    i)    Color  in  mass Hack 

(Test    2)    Homogeneity. Uniform 

(Test    3)     Appearance  surface  aged  indoors  one  week.  .   Dull 

(Test   4)     Fracture Conchoidal 

(Test    5)     Lustre Very  bright  when  fresh 

(Test    6)     Streak Black 

(Test   7)     Specific  gravity  at  77°  F i  .05-1 . 20 

(Test   9^)  Penetration  at  77°  F 0-60 

(Test   9f)  Hardness  at  77°  F.,  consistometer 10-100 

(Test   gd)  Susceptibility  index Greater  than  too 

(Test  10)     Ductility Variable 

(Test  150)  Fusing-point  (K.  and  S.  method) 90-250°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 100-275°  F. 

(Test  16)    Volatile  matter Variable 

(Test  ija)  Flash-point Usually  above  250°  F. 

(Test  19)    Fixed  carbon 10-40  per  cent 

(Test  21)    Solubility  in  carbon  disulfide 95-99  per  cent 

Non-mineral  matter  insoluble *    0-2  per  cent 

Mineral  matter o-  i  per  cent 

(Test  22)     Carbenes 0-5  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha.  .....   60-85  per  cent 

(Test  25)    Solubility  in  benzol 75-90  per  cent 

(Test  28)    Sulfur i .  5-2. 5  per  cent 

(Test  30)    Oxygen  in  non-mineral  matter 2-  5  per  cent 

(Test  31)    Free  carbon Trace 

(Test  32)    Naphthalene Absent 

(Test  33)    Solid  paraffins i-  5  per  cent 

(Test  34^)  Sulfonation  residue 5-15  per  cent 

(Test  37*)  Saponifiable  constituents o-  8  per  cent 

(Test  39)    Diazo  reaction Yes 

(Test  40)    Anthraquinone  reaction No 

(Test  41)    Liebermann-Storch  reaction No 


XV  LIGNITE  TAR  AND  LIGNITE-TAR  PITCH  323 

The  following  figures  are  reported  by  Julius  Marcusson  :10 


(Test    9)    Hardness  

STRAIGHT- 
DISTILLED 
LIGNITE-TAR 
PITCH 

.  .  .  .  .  M  oderatelv  hard 

LIGNITE-TAR 
PITCH 
DERIVED  FROM 
ACID-SLUDGE 

Hard  and  brittle 
i9oi°  F. 
20  per  cent 
>  2  per  cent 
4-4 
13-4 
6.0  per  cent 
36  per  cent 
8  per  cent 
26  per  cent 

(Test  150)  Fusing-point  (K.  and  S.  method)88°  F. 
(Test  24)    Free  carbon  ,  *  .  ,  .  -     1  1  t5*r  cent 

(Test  28)     Sulfur  

<  2  per  cent 

(Test  374)  Acid  value  

o,  c 

(Test  37^)  Saponification  value  .  . 

2.8 

(Test  37^)  Saponifiable  constituem 
(Test  38^)  Asphaltenes  

ts   ....     1.8  per  cent 

24  per  cent 

(Test  38^)  Asphaltic  resins  

ii  per  cent 

(Test  38*)  Oily  constituents*.  .  .  . 

48  per  cent 

*  Salve-like; 

light  brown  color. 

Soft  lignite-tar  pitch  is  almost  completely  soluble  in  benzol  and 
turpentine,  and  less  soluble  in  petroleum  benzine  or  naphtha.  The 
solubility  of  hard  pitches  decreases  in  proportion  to  the  extent  they 
have  been  distilled.  Lignite-tar  pitch  derived  from  acid  sludge  may 
be  distinguished  from  straight-distilled  pitches  by  the  presence  of 
sulf uric-acid  oxonium  derivatives  insoluble  in  88°  petroleum  naph- 
tha, as  is  the  case  with  sludge  asphalts  derived  from  petroleum.  Lig- 
nite-tar pitches  are  distinguished  from  coal-tar  pitches  by  the  ab- 
sence of  anthracene,  the  presence  of  small  quantities  of  paraffin  wax, 
and  the  formation  of  water-insoluble  sulfo-derivatives  upon  treat- 
ment with  concentrated  sulf  uric  acid  (whereas  coal-tar  pitches  form 
soluble  derivatives).  Furthermore,  the  free-carbon  separated 
from  lignite-tar  pitches  differs  from  that  obtained  from  coal-tar 
pitches  by  the  fact  that  the  former  is  completely  converted  into 
soluble  nitro-derivatives  upon  heating  with  fuming  nitric  acid.  Lig- 
nite-tar pitches  are  distingished  from  wood-tar  pitches  by  the  asso- 
ciated sulfur  and  paraffin  wax;  also  from  asphalts,  rosin  pitch  and 
fatty-acid  pitch  by  the  diazo  reaction.11 

A  process  of  blowing  lignite  tar  with  air  in,  the  presence  of 
mineral  substances  has  been  patented.12  It  has  also  been  proposed 
to  blow  a  mixture  of  lignite-tar  pitch  and  refined  Trinidad  asphalt.18 
Lignite  tars  may  be  hardened  by  heating  with  sulfur,14  or  by  heat- 
ing with  spent  iron  oxide  containing  sulfur  (obtained  in  the  puri- 
fication of  coal  gas)  in  the  presence  of  FeQ3,  MnSO4,  or  the  like.18 
In  Germany,  where  practically  all  of  the  lignite-tar  pitch  is  pro- 
duced, it  is  used  extensively  for  manufacturing  cheap  paints. 


CHAPTER  XVI 
SHALE  TAR  AND  SHALE-TAR  PITCH 

Shale  Mining.  Scotland  is  the  home  of  the  "shale  oil"  indus- 
try. The  present  chapter  is  based  on  the  operations  practiced  in 
Scotland,  since  in  other  countries  the  treatment  of  shales  has  not 
been  developed  to  what  may  be  regarded  as  an  industry  scale.  In 
the  United  States,  for  example,  the  distillation  of  shales  is  more 
or  less  in  a  process  of  development,  and  at  the  present  writing  is 
still  in  an  experimental  stage. 

At  the  present  time,  Scotch  refineries  are  located  at  Pumphers- 
ton,  Broxburn,  Oakbank,  Addiewell  and  Uphall ;  crude-oil  works  at 
Addiewell,  Broxburn,  Dalmeny,  Deans,  Hopetoun,  Niddry  Castle, 
Oakbank,  Philipstoun,  Pumpherston,  Roman  Camp,  Seafield,  Tar- 
brax  and  Uphall;  and  candle  works  at  Addiewell  and  Broxburn. 

Shale  is  mined  in  the  same  manner  as  bituminous  coal,  by  driving 
shafts,  and  then  extending  drifts  radially.  Considerable  timbering 
is  necessary,  on  account  of  the  softness  of  the  shale.  When  the 
seams  are  over  4  ft.  in  thickness,  they  are  mined  by  the  "pillar-and- 
stall"  method,  and  when  less  than  4  ft.  thick,  by  the  "longwall" 
method. 

The  mineral  as  mined  is  hauled  to  the  surface  by  power,  and 
then  run  through  a  breaker,  where  the  masses  are  broken  into  lumps 
measuring  4  to  6  in.  in  diameter.  The  breakers  consist  of  a  number 
of  toothed  iron  discs  mounted  on  two  shafts  revolving  in  opposite 
directions.  The  shale,  upon  being  crushed  to  the  proper  size,  is  next 
conveyed  up  an  iacline  to  the  top  of  the  retort. 

Retorts  Used  for  Distillation.  The  retorts  used  have  been  modi- 
fied from  time  to  time  to  increase  their  efficiency,  add  to  their  dura- 
bility, hasten  the  speed  of  treatment,  or  to  improve  the  quality  of 
the  output.  In  all  instances  the  distillation  takes  place  in  the  upper 
part  of  the  retort  where  the  shale  is  heated  to  900°  F.  It  is  then 
subjected  to  a  higher  temperature  (1300  to  1800°  F.)  in  the  lower 
portion,  which  is  in  reality  a  gas  producer,  steam  and  air  being 

824 


XVI 


SHALE  DISTILLATION 


325 


admitted  to  convert  the  carbonaceous  residue  into  carbon  dioxide 
and  carbon  monoxide.  This  generates  sufficient  heat  to  effect  the 
distillation  in  the  upper  portion  of  the  retort.  The  admission  of  air 
is  carefully  regulated  to  maintain  the  required  temperature,  with- 
out causing  excessive  combustion  of  the  by-products.  The  steam 
serves  to  convert  the  nitrogen  into  ammonia,  increases  the  value  of 
the  shale  tar,  dilutes  the  gas  vapors,  increases  the  velocity  of  the 
discharge,  reduces  the  secondary  decomposition  of  the  vapors,  in- 
creases the  yield  of  paraffin  products,  and  equalizes  the  temperature. 


'1  ' 


FIG.  98. — ^View  of  Pumpherston  Works,  Showing  Mine-head,  Retorts  and  Refinery. 

The  charge  gradually  passes  downward  in  the  retort  at  a  speed 
regulated  by  the  removal  of  the  spent  shale  at  the  bottom. 

At  present,  the  tendency  seems  to  gravitate  towards  the  use  of 
two  types  of  retorts,  viz.:  the  Pumpherston  and  the  Henderson 
retorts,  of  which  the  former  is  considered  to  be  the  more  efficient. 
Both  types  will  now  be  described. 

Pumpherston  Retort.  A  view  of  the  Pumpherston  works, 
showing  the  retorts  and  refinery  is  given  in  Fig.  98.  A  bank  of  the 
retorts  is  illustrated  in  Fig.  99,  and  the  equipment  for  condensing 
the  oils  and  ammoniacal  liquors  from  the  gases  emanating  from  the 
retorts  is  shown  in  Fig.  100.  Similarly,  a  cross-section  of  a  Pum- 
pherston retort  is  given  in  Fig.  101.  The  shale  is  prevented  from 


326 


SHALE  TAR  AND  SHALE-TAR  PITCH 


XVI 


Fia  99. — Bank  of  Scottish  Shale  Retorts  (Pumpherston  Type). 


FIG.  loo. — Plant  for  Condensing  Shale  Tar  and  Ammonia  Water  Emanating  from  the 

Shale. 


XVI 


SHALE  DISTILLATION 


fluxing  and  choking  up  the  retort 
by  keeping  it  moving  continuously, 
which  is  accomplished  by  support- 
ing the  column  of  shale  on  a  disc 
e,  from  which  a  revolving  scraper 
/  discharges  the  spent  shale  into 
the  hopper  below.  The  shale  is 
introduced  into  an  iron-charging 
hopper  c,  whence  it  passes  into 
the  upper  cylindrical  cast-iron  por- 
tion of  the  retort  a,  measuring 
1 1  ft.  high,  2  ft.  in  diameter  at 
the  top  and  2  ft.  4  in.  at  the  bot- 
tom. In  this,  the  actual  distilla- 
tion takes  place  at  900°  F.,  with 
the  formation  of  oil  and  gas.  The 
shale  slowly  works  its  way  into 
the  lower  portion  b  constructed 
of  firebrick,  of  circular  cross-sec- 
tion, measuring  20  ft  in  height 
and  enlarged  at  the  bottom  to  3 
ft.  in  diameter,  and  finally  into 
the  lower  hopper  d  extending  un- 
derneath several  retorts,  converg- 
ing in  such  a  manner  that  a  single 
line  of  rails  running  below  the 
center  will  permit  the  spent  shale 
to  discharge  into  small  cars. 
Steam  is  introduced  into  the 
lower  portion  of  the  retort,  a 
short  distance  above  the  disc  e, 
and  the  gaseous  products  of  dis- 
tillation are  burned  with  air  in  the 
external  flues  at  1800°  F.  in  the 
zone  b  where  the  ammonia  is 
formed.  The  daily  capacity  of 
the  retort  is  4  to  4^4  tons,  de- 
pending upon  the  richness  of  the 
shale.  Four  retorts  constitute  an 


FIG.   101. — Pumpherston  Type  of  Retort 
for  Distilling  Shale. 


828 


SHALE  TAR  AND  SHALE-TAR  PITCH 


XVI 


DD 


FIG.  102. — Broxburn  Type  of  Retort  for  Distilling  Shale* 


XVI  METHODS  OF  RECOVERING  SHALE  TAR  329 

"oven,"  and  16  ovens  a  "bench.*1  The  maximum  output  of  shale 
oil  amounts  to  96  gal.  per  retort  per  day  under  the  best  operating 
conditions. 

Henderson  or  Broxburn  Retort.  This  is  illustrated  in  Fig.  102, 
and  consists  of  iron  hoppers  a  on  top,  into  which  the  crushed  shale 
is  fed,  next  a  rectangular  cast-iron  section  b  measuring  2  f t.  9 1/2  in* 
by  i  f  t  2  y%  in.  at  the  top,  and  3  ft  J4  *n-  by  I  f  t.  5  %  in.  at  the 
bottom.  This  is  14  ft.  long,  and  is  joined  by  a  fire-clay  joint  to  a 
fire-brick  section  c,  20  ft.  long,  of  rectangular  cross-section,  measur- 
ing 4  ft.  8  in.  by  i  ft.  10  in.  at  the  bottom.  A  pair  of  toothed  iron 
rollers  d  continuously  discharge  the  spent  shale  from  the  bottom 
into  hoppers  e,  which  are  periodically  emptied  into  cars  under- 
neath. The  vapors  pass  out  at  the  top  through  the  ducts  /,  into 
headers  g.  A  slight  vacuum  is  maintained  in  the  retort  and  steam 
is  admitted  into  the  bottom  of  the  fire-brick  portion.  The  tempera- 
ture reaches  900°  F.  in  the  upper  cast-iron  section,  where  practically 
all  the  oil  is  distilled,  and  the  shale  is  subjected  to  an  increasing 
temperature,  reaching  a  maximum  of  1500°  F,  at  the  lower  portion 
of  the  fire-brick  section,  whereupon  it  is  cooled  by  the  incoming 
steam  before  it  is  discharged.  The  retorts  are  heated  by  the  fixed 
gases  evolved  from  the  shale,  supplanted  by  a  proportion  of  pro- 
ducer gas.  The  arrangement  of  the  retorts  in  benches  and  ovens, 
also  the  output,  is  the  same  for  the  Pumpherston  type.1 

Methods  of  Recovering  Shale  Tar.  The  vapors  which  leave  the 
retorts  are  passed  through  air-cooled  pipes  (Fig.  100)  which  sep- 
arate most  of  the  tar  and  ammoniacal  liquor.  Sometimes  an  econ- 
omizer is  used,  consisting  of  a  tower  filler  with  pipes,  around  which 
cold  water  is  circulated,  and  thus  preheated  for  use  in  the  steam 
plant  The  vapors  are  next  passed  through  a  scrubber  (filled  with 
coke  or  a  checker-work  of  wood),  and  finally  through  a  naphtha 
scrubber  where  they  are  washed  with  the  " intermediate  oil"  ob- 
tained in  distilling  the  shale  tar  (having  a  high  boiling-point  and 
a  specific  gravity  of  0.84  to  0.86)  which  extracts  any  light  naphtha 
not  previously  condensed  (about  2  gal.  per  ton  of  shale).  The 
naphtha  is  separated  from  the  scrubbing  oil  by  heating  the  mixture 
moderately  in  a  still,  and  condensing  the  distillate  (having  a  specific 
gravity  of  0.73)* 


380  SHALE  TAR  AND  SHALE-TAR  PITCH  XVI 

The  crude  tar  and  ammoniacal  liquor  are  allowed  to  flow  from 
the  condensers  to  separating  tanks,  where  upon  standing,  the  tar 
rises  to  the  surface  and  is  drawn  off  and  piped  to  the  refinery*  The 
crude  tar  is  generally  termed  "shale  oil/'  but  this  name  is  just  as 
inappropriate  as  the  expression  "oil  shale,"  often  used  to  designate 
the  shale* 

Products  Obtained.  Upon  destructively  distilling  the  Kim- 
meridge  Shales  of  England  and  the  Lothian  Shales  of  Scotland, 
the  following  products  are  obtained : 

(1)  Non-condensable  gases,  averaging  9800  cu.  ft  per  ton 
(2000  Ib.). 

( 2 )  Ammoniacal  liquor  yielding  an  average  of  40  Ib.  ammonium 
sulfate  per  ton. 

(3)  Shale  tar,  Averaging  22  gal.  per  ton. 

(4)  Scrubber  naphtha,  averaging  0.4  gal.  per  ton. 

(5)  Spent  shale,  averaging  between  75  and  85  per  cent  of  the 
raw  shale  (i.e.,  1500  to  1600  Ib.  per  ton),  and  containing  approxi- 
mately 2j^  per  cent  unconsumed  carbon. 

The  non-condensable  gases  are  burned  under  the  retorts,  and 
the  spent  shale  discarded,  as  it  has  no  further  value.  The  valuable 
products  are  the  light  naphtha,  the  shale  tar  and  ammonium 
sulfate. 

The  ammoniacal  liquor  separated  from  the  tar  is  treated  with 
steam  under  a  pressure  of  20  to  30  Ib.  in  a  tower  filled  with  baffle- 
plates.  The  liquor  is  run  in  at  the  top  and  the  steam  introduced  at 
the  bottom.  The  ammonia  is  expelled  in  the  gaseous  state  and  re- 
covered by  passing  it  into  sulfuric  acid  contained  in  a  vessel  known 
as  a  "cracker  box."  The  acid  used  for  this  purpose  is  usually  the 
waste  product  from  the  refining  process.  Crystals  of  ammonium 
sulfate  separate  when  the  liquor  becomes  sufficiently  concentrated, 
and  after  being  dried  are  marketed  as  such.  In  this  manner  the 
ammonia  is  separated  from  the  other  nitrogenous  bases,  including 
pyridine,  contained  in  the  aqueous  liquor. 

The  following  table  gives  the  minimum  and  the  maximum 
yields  of  dehydrated  shale  tar  in  gallons,  and  ammonium  sulfate  in 
pounds  per  ton  of  shale,  obtained  from  the  most  important  shate 
deposits  in  different  parts  of  the  world,2 


XVI 


PROPERTIES  OF  SHALE  TAR 


331 


Yield  of  Shale  Tar 
(Gallons) 


Yield  of  Ammonium 
Sulfate  (Pounds) 


Lothian  shale  (Scotland) 

Kimmeridge  shale  (England) 

Coorongitic  shale  (New  South  Wales) . 

Orepuki  shale  (New  Zealand) 

Albert  shale  (New  Brunswick) 

Arcadian  shale  (Nova  Scotia) 

Shales  (Eastern  United  States) 

Utah  shales 

Colorado  and  Wyoming  shales 

Kukkersite  (Esthonia) 


ro-55 

10-40 

14-150 

20-40 

30-51 


4-45 

6-10 

10-68 

70-80 


6-70 
10-50 
20-30 

67-1 1 1 
9-40 
o-io 

40-50 

22-34 

5-15 


Properties  of  Shale  Tar.  Shale  tar  usually  appears  black  in  mass 
with  a  greenish  fluorescence.  It  is  similar  in  composition  to  lignite 
tar,  although  differing  from  the  latter  in  containing  a  larger  per- 
centage of  nitrogen  (i.i  to  1.5  per  cent).  -Members  of  the  paraf- 
fin and  olefine  series  constitute  80  to  90  per  cent  by  weight  of  the 
tar,  and  small  quantities  of  cresols  and  phenols  are  present 

Dehydrated  shale  tar  tests  as  follows: 

(Test    i)     Color  in  mass , Brownish  black  with  a 

greenish  fluorescence 

(Test    7)     Specific  gravity  at  77°  F o.  85-0.95 

(Test    9)    Hardness  or  consistency Salve-like  to  buttery 

(Test  150)  Fusing-point  (K.  and  S.  method) 60-90°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 75~n  5°  F. 

(Test  1 6)    Volatile  matter  at  500°  F.,  5  hrs 80-90  per  cent 

(Test  ija)  Flash-point  (Pensky-Martens  tester) 20-60°  F. 

(Test  19)     Fixed  carbon 5-10  per  cent 

(Test  21)     Soluble  in  carbon  disulfide 98-100  per  cent 

Non-mineral  matter  insoluble 0-2  per  cent 

Mineral  matter o-i  per  cent 

(Test  22)     Carbenes 0-2  per  cent 

(Test  23)     Soluble  in  88°  petroleum  naphtha 95-100  per  cent 

(Test  24)     Free  carbon 0-2  per  cent 

(Test  28)     Sulfur i . 5-2. 5  per  cent 

(Test  29)    Nitrogen o. 25-1  .o  per  cent 

(Test  30)    Oxygen 1-5  per  cent 

(Test  33)     Solid  paraffins 5-15  per  cent 

(Test  34^)  Sulfonation  residue I5~35  per  cent 

(Test  37?)  Saponifiable  constituents 0-2  per  cent 

(Test  39)    Diazo  reaction Yes 

(Test  40)    Anthraquinone  reaction No 

(Test  41)    Liebermann-Storch  reaction No 

The  percentage  of  phenols  contained  in  the  shale  tar  is  very 
much  smaller  proportionately  than  that  present  in  peat  or  lignite 


332  SHALE  TAR  AND  SHALE-TAR  PITCH  XVI 

tars.  Shale  tar  is  distinguished  from  the  latter  by  containing  larger 
percentages  of  nitrogen  and  sulfur,  and  smaller  percentages  of 
oxygen,  paraffin  and  phenols  respectively. 

Refining  of  Shale  Tar.  Shale  tar  may  be  distilled  either  inter- 
mittently or  continuously.  In  either  case  the  process  consists  in 
heating  the  tar  in  a  still  to  expel  the  moisture,  whereupon  either 
plain  or  superheated  st§am  is  introduced  through  a  perforated  pipe 
under  a  pressure  of  between  10  and  40  Ib.  The  tar  is  distilled  to 
coke  and  the  following  products  separated: 

1 i )  Non-condensable  gases  ranging  from  i  to  2  cu.  ft.  for  each 
gallon  of  shale  tar. 

(2)  Crude  naphtha  having  a  specific  gravity  of  0.74  to  0.76. 

(3)  So-called  "crude  distillate,"  or  "once-run  oil/'  or  "green 
oil"  representing  the  fraction  between  the  crude  naphtha  and  coke. 

(4)  A  residue  of  coke  approximating  3  per  cent  by  weight  of 
the  shale  tar. 

The  steam  is  shut  off  towards  the  end  of  the  distillation,  after  the 
"once-run  oil"  has  passed  over. 

The  stills  used  in  Scotland  are  of  the  vertical  type  from  2000  to 
2500  gal.  capacity,  constructed  of  a  hemispherical  cast-iron  bottom, 
and  a  soft  malleable-iron  cylindrical  body  to  which  is  attached  a 
dome-shaped  top  bearing  the  exit  pipe.  Each  still  is  connected  with 
its  own  condenser. 

In  the  continuous  distillation  process,  termed  the  "Henderson 
Process,"  a  battery  of  three  horizontal  stills  and  one  or  more  ver- 
tical pot-stills  are  used.  The  tar  is  first  led  into  the  middle  hori- 
zontal still  where  the  naphtha  is  distilled  off,  and  the  residue  caused 
to  flow  continuously  into  the  two  side  stills.  These  are  heated 
higher  than  the  center  still,  causing  the  one-run  oil  to  distil  over 
continuously.  The  residues  from  these  second  stills  are  led  into  the 
pot-still,  where  they  are  evaporated  to  dryness,  the  distillate  being 
condensed  and  united  with  the  once-run  oil.  Several  pot-stills  are 
used,  since  the  red-hot  coke  must  be  allowed  to  cool  before  it  can  be 
removed,  which  prevents  this  part  of  the  process  being  continuous. 

The  once-run  oil  is  refined  by  agitating  it  with  sqlfuric  acid  at 
100°  F.  by  compressed  air.  The  acid  sludge  is  run  off,  the  oil 
washed  with  water,  and  then  treated  in  another  agitator  with  caus- 
tic soda  in  a  similar  manner* 


XVI  REFINING  OF  SHALE  TAR  333 

The  refined  once-run  oil  is  fractioned  either  by  an  intermittent 
or  continuous  steam  distillation  process,  the  following  products  be- 
ing recovered  : 

1 i )  Heavy  naphtha  varying  in  gravity  between  0.75  and  0.77. 

(2)  ^  Illuminating  oils  varying  in  gravity  between  0.78  and  0.85, 
and  having  a  flash-point  of  125°  F, 

(3)  Gas-oil  and  fuel-oils  varying  in  gravity  between  0.85  and 
0.87,  and  having  a  flash-point  higher  than  150°  F.    These  are  used 
as  fuel,  or  for  manufacturing  water-gas,  or  enriching  illuminating 
gas. 

(4)  Lubricating  oils  having  a  gravity  from  0.87  to  0.91. 

(5)  Paraffin   wax  which   is   purified   by  re-crystallization   or 
"sweating,1*  having  a  fusing-point  between  110  and  130°  F. 

(6)  Still  grease,  which  represents  the  distillate  passing  over  at 
the  close  of  the  distillation. 

(7)  Still  coke,  which  remains  in  the  still  at  the  close  of  the 
operation. 

The  various  distillates,  with  the  exception  of  the  still  grease  are 
refined  further  with  sulfuric  acid  and  caustic  soda,  similar  to  the 
method  used  for  treating  the  once-run  oil.  The  crude  paraffin  wax 
is  refined  by  the  sweating  process. 

The  various  steps  of  the  distillation  and  refining  processes  are 
illustrated  in  Table  XXII. 

The  following  yields  are  obtained  from  dehydrated  Scotch  shale 
tar: 

Heavy  and  light  naphthas 3-6  per  cent 

Illuminating  oil 20-30  per  cent 

Gas-oil  or  fuel-oil 10-25  per  cent 

Lubricating  oil > 1 5-20  per  cent 

Soft  paraffin  scale 3-5  per  cent 

Hard  paraffin  wax 7-9  per  cent 

Non-condensable  gases 3-5  per  cent 

Acid  and  soda  sludges  and  losses t . . .  20-25  per  cent 

Still  coke 2-3  per  cent 

The  acid  and  soda  tars  obtained  from  the  various  refining 
processes  are  mixed  together  in  such  proportions  that  the  free  acid 
and  alkali  will  exactly  neutralize  each  other.  The  resulting  sludge 
is  ordinarily  used  as  fuel  for  the  stills,  but  experiments  have  been 
made  to  convert  it  into  pitch  suitable  for  use  as  a  wood  preserva- 
tive, pipe-dip,  or  the  base  of  bituminous  paints.  Comparatively 


334 


SHALE  TAR  AND  SHALE-TAR  PITCH 


XVI 


TABLE  XXII 

FLOW  SHEET  ILLUSTRATING  THE  METHOD  OF  MANUFACTURE  OF  OILS,  PARAFFIN  WAX  AND 
SULFATE  OF  AMMONIA  FROM  SHALE.  THE  NAMES  OF  FINISHED  PRODUCTS  ARE  UNDER- 
LINED 

SHALE 


Liq 


Scrubber 
Naphtha 

Treated  &  Distd. 


Shale 
Tar 


Shale 


Swfate 

otArrimoriia 

Motor 

3E# 

Wed 

Cfude 
Naphtha 

TreatedWisrd 

Cn 

Treated 

t 
IS 

de                            Shale                   CoJ* 
Hate                          Rasm 

tOtstd. 

Ctoaners* 

So/Wf 

Crbdc 
Burning 

HeavyOtl                              \ 
contain/no                        CoAe 
Solid  paraffin 

la/no       fbber         Signal     tJtoise  Crude 
~         "O/L         M 


Cooled,  filtered 3  pressed 


B/ue-Ofl 

Treattd&Distd 


J$$d 
faMffin 

Cooled,  Filtered 


Baiching  Lao.  Oil 

OH&Sonet  QSolid 

Paraffin  Paraffin' 

Cooted,rtHer*d  Cookd.fi  fared 
$ 


UMll      Solid 
VnM  Paraffin 

'"  \    -' 


Residuum 
Oil 


XVI  REFINING  OF  SHALE  TAR  335 

little  has  been  accomplished  in  this  direction,  probably  due  to  the 
fact  that  other  products  are  available  for  these  purposes,  costing 
but  little  more  and  possessing  superior  weather-resisting  properties. 
Shale-tar  pitch  is  similar  in  its  physical  properties  and  composition 
to  lignite-tar  pitch, 

A  residue  derived  from  Esthonian  shale  oil  (obtained  by  the 
destructive  distillation  of  Esthonian  "kukkersite" )  has  been  termed 
"esto-bitumen"  or  "esto-asphalt,"  which  unlike  paraffin  petroleum 
asphalts  is  completely  miscible  with  coal  tar  in  all  proportions.8 


CHAPTER  XVII 
COAL  TAR  AND  COAL-TAR  PITCH 

Under  the  headings  "Coal  tar"  and  "Coal-tar  pitch/'  will  be 
included  t^e  tars  and  corresponding  pitches  recovered  as  by-products 
from  bituminous  coal  *  in : 

i)  Gas  works; 

2}  Coke  ovens; 

3)  Blast  furnaces; 

4;  Gas  producers; 

5)   Low-temperature  processes. 

* 

Water-gas  tar  and  water-gas-tar  pitch  have  been  included  by 
some  writers  within  the  scope  of  the  terms  coal  tar  and  coal-tar  pitch 
respectively,  but  in  this  treatise  they  will  be  considered  separately, 
since  they  differ  in  their  composition  and  properties,  due  to  the  use 
of  petroleum  products  in  their  manufacture. 

Bituminous  Coals  Used.  Bituminous  coals  only  are  suitable  for 
the  production  of  coal  tar.  Cannel,  bog-head  and  anthracite  coals 
will  not  answer,  since  the  former  distils  at  too  low  a  temperature, 
and  the  latter  contains  insufficient  volatile  matter.  Upon  subject- 
ing cannel  coal  to  low-temperature  distillation,  there  is  obtained  20 
to  40  per  cent  of  cannel-coal  tar  having  a  specific  gravity  at  50°  C. 
of  0.9,  containing  much  paraffin  and  5  to  10  per  cent  phenols.  At 
20°  C.  cannel-coal  tar  has  the  consistency  of  butter.  Upon  subject- 
ing bog-head  coal  to  low-temperature  distillation,  30  to  60  per  cent 
of  tar  is  produced,  having  a  thick,  salve-like  consistency  and  con- 
taining solid  paraffins,  phenols  and  naphthenes,  but  no  naphthalene 
or  anthracene.  It  is  known  as  bog-head-coal  tar.  Torbanite  on 
distillation  yields  20  to  35  per  cent  of  torbanite  tar  having  a  spe- 
cific gravity  at  35  °-  C.  of  0.90  to  0.95,  and  containing  phenols  and 
a  small  amount  of  solid  paraffin. 

Bituminous  coals  are  known  as  "gas  coals'*  when  used  for  manu- 
facturing illuminating  gas,  and  "coking  coals"  when  used  for  coking. 
Western  Pennsylvania,  West  Virginia,  Virginia,  eastern  Kentucky 

836 


XVII  TEMPERATURE  OF  TREATMENT  337 

and  Tennessee  produce  most  of  the  bituminous  coals  used  for  these 
purposes,  and  they  comply  with  the  following  characteristics: 

Air-dry  loss  of  coarse  material i    -5  per  cent 

Moisture  at  105°  C.  (powdered  material) i . 5-7.0  per  cent 

Volatile  matter  on  ignition 20  -40  per  cent 

Fixed  carbon 50  -75  per  cent 

Ash Less  than  1 5  per  cent 

Sulfur . . , .  Less  than  a  per  cent 

Hydrogen 4. 5-5. 5  per  cent 

Carbon 65-85  per  cent 

Nitrogen i~2  per  cent 

'  Oxygen 5-1 5  per  cent 

Very  little  is  known  regarding  the  chemical  composition  of  the 
bituminous  coal  itself,  due  to  the  difficulty  in  converting  the  coal 
into  recognizable  derivatives,  and  because  of  its  slight  solubility  in 
the  usual  solvents  for  bituminous  materials.  On  subjecting  coal  to 
high  temperatures,  the  bodies  present  decompose  into  simpler  sub- 
stances which  fail  to  give  any  clue  as  to  their  original  structure  and 
composition.  Recent  researches  lead  to  the  conclusion  that  coal  is 
essentially  a  conglomerate  of  cellulose  decomposition  products,  ad- 
mixed with  altered  resins  and  gums  originally  present  in  the  plants 
from  which  the  coal  was  derived. 

Temperature  of  Treatment.  D.  T.  Jones  examined  the  tars 
derived  from  the  destructive  distillation  of  bituminous  coal  in  vacuo 
at  very  low  temperatures  (below  450°  C.).  These  were  then  sub- 
jected at  atmospheric  pressure  to  successively  increased  tempera- 
tures up  to  800°  C.  Unsaturated  hydrocarbons,  naphthenes,  paraf- 
fins, phenols,  aromatic  hydrocarbons  and  pyridines  were  found  to 
be  present  in  the  low-temperature  tar,  whereas  benzol  and  its  homo- 
logues,  naphthalene,  anthracene,  phenanthrene  and  the  solid  aro* 
matic  bodies  were  absent.  As  the  temperature  was  increased,  the 
naphthenes,  paraffins,  and  unsaturated  hydrocarbons  were  trans- 
formed into  olefines.  As  the  temperature  was  further  increased, 
the  olefines  were  in  turn  transformed  into  benzene  and  its  homo- 
logues.  The  percentage  of  olefines  appears  to  reach  a  maximum 
at  550°  C.,  and  a  minimum  at  750°  C.,  at  fahich  latter  temperature 
hydrogen  and  naphthalene  are  rapidly  evolved^  as  well  as  methane. 
The  conclusion  reached  is  that  ordinary  coal  tar  obtained  from 
bituminous  coal  at  high  temperatures  results  chiefly  from  tlie  de- 
composition of  the  tar  previously  formed  at  lower  temperatures. 


338 


COAL  TAR  AND  COAL-TAR  PITCH 


XVII 


The  following  figures  will  give  a  rough  idea  of  the  effect  of  the 
temperature  on  the  yield  and  characteristics  of  the  tar  produced 
from  an  average  grade  of  British  coal : 


Tempera- 
ture 

Tar 

(Gals: 
per  Ton) 

Sp.  Gr. 
Tar  at 
77°  F, 

Free 
Carbon 
in  Tar, 
Per  Cent 

Distillate  to  315°  C. 

Pitch 
(Per 
Cent  by 
Weight) 

Naph- 
thalene, 
Per  Cent 

Paraffin, 
Per  Cent 

Coke-ovens  (narrow)  

1300°  C. 
1100-1350°  C. 
900-1200°  C. 
1000-1100°  C. 
1000-1200°  C. 
400-700°  C. 

8.0 
9-5 

11.  0 
12.  0 
15-5 
18.3 

1.210 
I.  200 
I.I90 

1.  155 
1.  100 
1.  035 

20 
IS 

14 

12 

5.5 
I 

30-35 

20-30 
15-20 
5-12 

<5 

o 

o 
o 
Trace 

5 
13 
25 

72 
'     66 
65 
58 
48 
40 

Horizontal  retort  

Inclined  retort  

Vertical  retort  ,.,..,..* 

Low-temperature  carbonization 

By  low-temperature  carbonization  of  coal  is  meant  its  destruc- 
tive distillation  under ^700  to  800°  C.  Below  this  temperature 
range  there  are  evolved  mostly  condensable  tars  and  oils,  with  a 
minimum  of  fixed  gases;  whereas  above  this  range,  mostly  fixed 
gases  are  produced,  due  to  secondary  reactions.  This  is  illustrated 
.by  the  following  figures  applicable  to  i  ton  of  average  coal  con- 
taining 25  to  30  per  cent  volatile  matter: 


Low-temperature 
(Coalite  Process) 

High-temperature  Processes 

Gas  Works 

Coke  Ovens 

Temperature  of  vapors.  ..... 
Yield  gas           

550°  C 
6,000-6,500   cu.    ft. 
rich  gas  (700-750 
B.t.u.) 
lo  gal.  tar  (*) 
15  Ib. 
14  cwt. 

1,000°  C. 
12,000  cu.ft.  medium 
gas  (550  B.t.u.) 

10  gal.  tar 
25  Ib. 
13$  cwt. 

1,200°  C. 

11,500  cu.  ft.  lean 
gas  (450  B.t.u.) 

8  gal.  tar 
28  Ib. 
14-14$  cwt. 

Yield  liquid  products.  ....... 

Ammonium  sulfate  

Yield  coke  

*  Absence  of  naphthalene  and  anthracene  distinguish  this  tar  from  high-temperature  tars. 

The  percentage  yield  of  tar,  figured  on  the  weight  of  coal 
treated)  will  approximate  the  following: 

Gas  works  (horizontal  retort) 5-7  per  cent 

Gas  works  (vertical  retort) 4-6  per  cent 

Cokevovens 2-6  per  cent 

Low-temperature  carbonization 8-13  per  cent 

ation *.,..* 5"IQ  Pcr  cent 


XVII 


PRODUCTION  OF  GAS- WORKS  COAL  TAR 


339 


The  commercial  processes  for  obtaining  coal  tar  will  now  be 
considered. 

Production  of  Gas-works  Coal  Tar.  In  manufacturing  illumi- 
nating gas,  bituminous  coal  is  heated  in  comparatively  small  fire- 


I 

t/5 

rt 

o 

2 
c 

s 


clay  retorts,  of  D-shaped,  oval  or  round  cross-section  about  16  to 
24  in.  in  diameter.     The  D-shaped  retort  is  ordinarily  used  in 


840  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

modern  gas-works  because  it  is  least  liable  to  distortion  under  the 
>action  of  heat,  and  moreover  presents  the  greatest  area  at  its  base, 
enabling  the  contents  to  be  heated  more  rapidly.  In  some  cases  the 
retorts  are  ''single-ended,"  measuring  8  to  9  ft.  in  length,  but  mod- 
ern practice  favors  the  use  of  "double-ended"  retorts  composed  of 
three  Sections  joined  together,  measuring  15  to  25  ft  over  all.  In 
the  single-ended  retort  a  metal  mouthpiece  is  bolted  to  one  end,  to 
which  in  turn  the  gas  outlet  pipe  is  fastened.  With  the  double- 
ended  retort,  metal  mouth-pieces  are  bolted  fast  to  both  ends,  From 
6  to  9  retorts  are  set  together  in  a  common  brick  setting,  consti- 
tuting a  "bench"  which  is  heated  by  a  single  furnace. 

Retorts  Used.  The  retorts  are  supported  in  either  a  horizon- 
tal, inclinfed  of  vertical  position.  The  inclined  or  vertical  retorts 
seem  to  meet  with  greater  favor  since  they  avoid  overheating,  pre- 
vent the  formation  of  "free  carbon"  in  the  tar,  and  at  the  same 
time  permit  the  coke  to  be  handled  by  gravity.  The  vapors  leave 
horizontal  retorts  at  1600  to  1800°  F.  and  the  vertical  and  inclined 
retorts  at  1300  to  1400°  F. 

The  retorts  are  heated  with  water-gas  obtained  by  passing  air 
and  steam  through  incandescent  coke  beneath  the  "bench."  The 
coke  used  for  this  purpose  is  derived  as  a  residue  from  a  previous 
charge  of  bituminous  coal,  amounting  to  15  to  25  per  cent  of  the 
total  coke  produced.  The  water-gas  is  burnt  in  flues  surrounding  the 
retorts  and  the  process  of  combustion  controlled  by  the  introduction 
of  air.  This  method  of  firing  results  in  a  higher  and  more  uniform 
terfiperature  with  the  minimum  consumption  of  fuel.  The  tempera- 
ture in  the  combustion  chamber  ranges  from  2800  to  3200°  F.,  and 
in  the  flues  surrounding  the  retorts  from  1900  to  2200°  F.  An  im- 
proved installation  of  horizontal  retorts  is  shown  in  Fig.  103,  in- 
clined retorts  in  Fig.  104,  and  vertical  retorts  in  Fig.  105.  Con- 
tinuously operating. vertical  retorts  are  now  being  adopted  exten- 
sively, in  which  the  coal  is  fed  through  the  retort  in  a  constant 
stream,  the  coke  being  withdrawn  continuously  at  the  bottom. 

Formerly,  the  retorts  were  charged  and  discharged  by  hand, 
using  a  shovel  and  rake  respectively.  Mechanical  devices  are  now 
used  for  the  purpose,  the  double-ended  horizontal  retorts  being 
charged ;*£ both^tids  with  a  scoop,  fed  from  an  overhead  hopper, 
operated  ei thereby, compressed  air  or  electricity.  About  600  Ib,  of 


XVII 


PRODUCTION  OF  GAS-WORKS  COAL  TAR 


341 


coal  are  introduced  into  the  double-ended  retort,  and  subjected  to 
heat  from  3  to  6  hours.  The  inclined  and  vertical  retorts  are 
charged  through  the  top  and  discharged  by  gravity  from  the  lower 
end.  Horizontal  retorts  are  discharged  by  a  pneumatic  or  an  elec- 
trically driven  ram,  which 
forces  out  the  coke  at  the  far- 
ther end.  Inclined  retorts  are 
set  at  an  angle  between  25  and 
35°,  which  is  sufficient  to  en- 
able the  coal  to  feed  into  the 
lowrer  end,  where  it  is  held  in 
place  by  a  metal  cover.  In 
the  inclined  and  vertical  types 
the  volatile  constituents  are 
withdrawn  from  the  upper 
end. 

The  vapors  are  subjected 
to  the  highest  temperatures  in 
the  horizontal  retort,  due  to 
the  longer  contact  with  the 
heated  internal  surfaces, 
which  results  in  a  larger  per- 
centage of  free  carbon,  and  a 
tar  of  higher  specific  gravity. 

Methods  of  Recovering 
Gas-works  Coal  Tar.  The 
volatile  products  pass  from 
the  retort  into  the  hydraulic 
main,  which  forms  a  water- 
seal,  permitting  any  retort  to 
be  charged,  and  at  the  same 
time  preventing  the  gas  gen- 
erated in  the  other  retorts  es- 
caping through  the  open  one. 
The  hydraulic  main  reduces  the  temperature  of  the  vapors  to  130- 
160°  F. 

After  leaving  the  hydraulic  main  the  vapors  are  subjected  to 
the  following  treatment  in  modern  gas-works : 


From  "Coal  and  Coke,"  by  F.  H.  Wagner 
FIG.  104. — Inclined  Gas- Works  Retort. 


342 


COAL  TAR  AND  COAL- TAR  PITCH 


XVII 


(1)  The    gases    are   passed  through   a    "primary   condenser" 
which  may  either  be  air-cooled  or  water-cooled,  or  both. 

(2)  The  gases  are  then  passed  through  a  tar-extractor. 

(3)  Then  they  are  passed  through  an  exhauster  to  relieve  the 
pressure  on  the  retorts  and  force  the  gases  through  the  ensuing 
train  of  apparatus. 

(4)  The  gases  are  next  passed  through  two  "scrubbers,"  pref- 
erably of  the  rotary  type.    In  the  first  scrubber  the  gases  are  washed 
with  a  heavy  tar  oil,  such  as  anthracene  oil,  to  remove  the  naphtha- 


FlG,  105. — Vertical  Gas- Works  Retort. 

lene,  and  in  the  second  with  an  alkaline  solution  of  ferrous  sulfate 
to  remove  the  cyanogen. 

(5 )  The  gases  are  then  cooled  to  about  60°  F.  by  passing  them 
through  a  "secondary  condenser,"  similar  to  the  first  one. 

(6)  The  ammonia  is  next  removed  by  passing  the  gases  through 
a  third  scrubber  through  which  a  stream  of  water  is  allowed  to 
trickle.     Formerly  a  tower  scrubber  filled  with  a  checker-work  of 
wooden  boards  was  used  for  this  purpose,  but  this  is  being  replaced 
by  a  rotary  scrubber  similar  to  tnat  used  for  extracting  the  naph- 
thalene and  cyanogen. 


XVII  PRODUCTION  OF  GASWORKS  COAL  TAR  343 

(7)  The  last  step  consists  in  passing  the  gases  through  a  series 
of  "purifiers,"  consisting  of  low  cylindrical  chambers  llled  with 
trays  or  sieves.  Some  of  the  purifiers  are  filled  with  slaked  lime  to 
remove  carbon  dioxide  and  a  portion  of  the  sulfur  compounds,  and 
others  with  iron  oxide  to  remove  the  remainder  of  the  sulfur  com- 
pounds (mostly  hydrogen  sulfide). 

Products  Obtained.  The  following  percentages  of  tar  are  col- 
lected from  the  hydraulic  main,  condenser,  washer  and  scrubber, 
also  the  tar  extractor  respectively: 

Hydraulic  main 61  per  cent 

Condensers 12  per  cent 

Washer  and  scrubbers i  £  per  cent 

Tar  extractor 12  per  cent 

Total 100  per  cent 

The  operations  which  take  place  in  the  final  handling  of  illuminat- 
ing gas  before  it  enters  the  mains,  cease  to  be  of  interest  in  relation 
to  the  production  of  tar,  and  will  accordingly  be  omitted. 

In  the  United  States,  temperatures  to  which  the  retorts  are 
heated  vary  from  900  to  1500°  C.  In  England  the  average  tem- 
perature is  1 1 00°  C.  In  Germany  horizontal  retorts  are  heated 
between  1000  and  1 100°  C.,  and  inclined  retorts  between  1 100  and 
1200°  C.  The  quantity  and  yield  of  the  tar  depend  largely  upon 
the  temperature.  In  the  low-temperature  production  of  illuminating 
gas,  an  average  of  16  gal.  of  tar  is  produced  per  ton  of  coal,  and  in 
high  temperature  processes  an  average  of  8.  The  maximum  varia- 
tion ranges  between  4  and  20  gal.  of  tar  per  ton.  High-tempera- 
ture processes  are  preferable,  as  they  increase  the  yield  of  gas,  but 
have  the  disadvantage  of  reducing  its  illuminating  power. 

The  following  represent  the  yields  from  an  average  grade  of 
bituminous  coal  in  manufacturing  illuminating  gas: 

Gas 17  per  cent  (10,000  cu.  ft.) 

Aqueous  liquor 8  per  cent 

Tar 5  Fr  cent 

Coke 70  per  cent 

Total loo  per  cent 

Of  course,  these  figures  are  subject  to  variation,  and  depend 
upon  the  quality  of  bituminous  coal  used,  the  temperature  at  which 
it  is  distilled,  etc.  Thus  the  yield  of  gas  per  ton  of  rich  coal  will 
vary  from  5000  to  15,000  cu.  £tM  and  the  residual  coke  from  55  to 
75  per  cent. 


344  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

The  tar  collected  from  the  hydraulic  main,  condenser,  washers 
and  scrubbers  is  run  into  wells  constructed  of  metal  or  masonry, 
sometimes  heated  with  steam-coils  and  allowed  to  settle  as  long  as 
possible,  to  permit  the  aqueous  liquor,  which  is  lighter  than  the  tar, 
to  rise  to  the  surface,  where  it  is  drawn  off  and  treated  separately 
to  recover  the  ammonium  compounds.  The  well-settled  gas-works 
tar  carries  between  4  and  10  per  cent  of  water.  In  exceptional 
cases  the  water  may  run  a$  high  as  40  per  cent,  although  this  is  not 
regarded  with  favor. 

Production  of  Coke-Oven  Coal  Tar. 2  As  stated  previously, 
about  78  per  cent  of  the  coal  tar  produced  annually  in  the  United 
States  is  obtained  from  coke-ovens  equipped  to  recover  by-products. 
This  only  represents  between  60  and  70  per  cent  of  the  total  quan- 
tity of  bituminous  coal  converted  into  coke.  The  remaining  30  to 
40  per  cent  is  coked  in  brick  "beehive"  ovens,  constructed  in  the 
form  of  a  beehive,  and  not  adapted  to  recover  the  gas,  ammonia  or 
tar,  which  are  allowed  to  burn  away  through  an  opening  iri  the  top 
of  the  oven,  thus  constituting  a  reckless  waste  of  our  national  re- 
sources, running  into  many  millions  of  dollars  annually.  For  years 
this  wasteful  practice  remained  unchecked,  but  happily  the  present 
tendency  is  to  replace  the  beehive  ovens  with  types  adapted  to 
recover  by-products,  and  it  is  probably  only  a  matter  of  a  few  years 
more  before  all  the  coke-ovens  will  be  equipped  to  recover  the  gas, 
ammonia  and  tar.  This  same  wasteful  tendency  is  reflected  in  a 
patent  granted  in  the  United  States  and  describing  the  production 
qf  coal-tar  pitch  by  the  simple  expedient  of  igniting  coal  tar  and  per- 
mitting the  more  volatile  constituents  to  burn  off  (sic!).8 

In  European  countries,  on  the  other  hand,  where  the  tendency 
has  always  been  towards  a  greater  economy,  coke-ovens  have  long 
been  perfected  to  recover  these  by-products.  In  this  connection  it 
must  be  borne  in  mind,  whereas  it  is  absolutely  necessary  to  remove 
the  tar  in  manufacturing  coal  gas  for  illuminating  purposes,  this 
does  not  prove  to  be  the  case  where  the  coal  is  converted  into  coke 
for  metallurgical  industries.  This,  and  the  comparative  cheapness 
of  bituminous  coal  in  the  United  States,  also  the  low  price  com- 
manded by  the  by-products  until  recently,  will  account  for  the  laxity 
4%  conserving  them. 

The  temperature  of  coking  varies  between  1000  and  1100°  C, 


XVII  PRODUCTION  OF  COKE-OVEN  COAL  TAR  345 

and  rarely  above  the  latter  inside  the  retort.  The  external  tempera- 
ture of  the  retort  may  run  as  high  as  1700°  C.  The  adaptability  of 
coal  for  coking  purposes  is  indicated  with  a  fair  degree  of  certainty 
by  the  ratio  of  hydrogen  to  oxygen,  together  with  the.  percentage 
of  fixed  carbon  calculated  on  the  moisture-free  basis.  Practically 
all  coals  with  an  H :  O  ratio  of  59  per  cent  or  over,  and  less  than  79 
per  cent  of  fixed  carbon,  possess  that  quality  of  fusion  and  swelling 
necessary  to  good  coking.  Bituminous  coals  with  a  ratio  down  to 
55  will  produce  a  more  or  less  satisfactory  coke,  whereas  coals  with 
a  ratio  as  low  as  50  are  unsuitable  for  coking  purposes. 

Retorts  Used.  The  present  systems  of  by-product  oven  con- 
struction resolve  themselves  into  two  types  depending  upon  whether 
the  flue  construction  is  horizontal  or  vertical.  In  either  type  the 
coking  takes  place  in  a  narrow,  retort-shaped  chamber  about  33  ft 
long,  from  17  to  22  in.  wide,  and  about  6l/2  ft.  high.  The  width 
of  the  chamber  averages  19  ft,  which  has  proven  suitable  for  com- 
pleting the  coking  within  twenty-four  hours.  The  retort  holds  be- 
tween 12  and  14  tons  of  coal. 

The  ends  of  the  retort  are  closed  by  means  of  iron  doors  lined 
with  fire  brick,  which  after  being  closed  as  tightly  as  possible  are 
luted  with  clay  to  prevent  the  entrance  of  air.  The  coal  is  charged 
into  the  top  of  the  oven,  then  pushed  into  place  and  leveled  by  me- 
chanical devices.  At  the  end  of  the  coking,  the  doors  are  opened 
and  the  coke  removed  by  a  ram,  the  red-hot  coke  being  immediately 
quenched  with  water. 

The  number  of  ovens  in  a  battery  varies  between  40  and  100, 
depending  upon  the  type  of  construction.  The  oven  walls  are  con- 
structed of  fire  brick  containing  about  95  per  cent  of  silica,  which 
on  account  of  its  very  high  fusing-point  enables  the  ovens  to  be 
worked  at  high  temperatures,  and  at  the  same  time  proves  to  be  an 
excellent  conductor  of  heat. 

For  a  detailed  description  of  the  various  types  of  coke-ovens 
in  use,  the  reader  is  referred  elsewhere. 

The  coking  in  the  by-product  oven  is  in  reality  a  destructive 
distillation  process,  the  heat  required  being  supplied  by  burning  a 
portion  of  the  gases  evolved.  A  large  excess  of  gas  is  produced 
amounting  to  between  40  and  60  per  cent  of  the  total 

Products  Obtained.  The  following  yields  per  ton  are  recovered : 


346  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

Gas. .......  t 15.0-16.0  per  cent  (8,500-10,500  cu.  ft.) 

Ammonium  sulfate 0.8-  1.3  per  cent 

Tar 3.0-  6.4  per  cent 

Coke 70.0-75.0  per  £ent 

Approximately  20  per  cent  of  the  nitrogen  present  in  the  coal  is 
converted  into  ammonium  compounds,  part  of  which  is  found  in 
the  tar  as  pyridine,  quinoline,  etc.  About  half  of  the  nitrogen  re- 
mains in  the  coke,  and  may  be  regarded  as  lost. 

The  vapors  emanating  from  the  coke-ovens  are  passed  through 
various  forms  of  condensers  and  scrubbers  to  separate  the  am- 
moniacal  liquor  and  tar,  which  are  sirhilar  to  those  used  in  gas 
works.  The  yield  of  tar  recovered  from  coke-ovens  varies  from  4 
to  15  gal.  per  ton,  depending  upon  the  kind  of  coal  used,  as  well  as 
the  type  of  coke-oven.  Over  90  per  cent  of  the  tar  (anhydrous) 
condenses  in  the  collector  main  and  primary  coolers,  2  per  cent  in 
the  exhausters,  and  7  per  cent  in  the  tax-extractor. 

The  following  constituents  have  been  identified  in  coke-oven 
coal  tar  produced  in  the  United  States : 4 

Light  oil:  Per  Cent 

Crude  benzene  and  toluol 0.3 

Coumarone,  mdene,  etc ' 0.6 

Xylenes,  cumenes  and  isomers •. i .  i 

Middle  and  heavy  oils: 

Naphthalene .  10.9 

Unidentified  oils  in  range  of  naphthalene  and  methylnaphthalenes  i .  7 

a-Monomethylnaphthalene I .  o 

j8-Monomethylnaphthalene 1.5 

Dimethylnaphthalenes ^ 3.4 

Acenaphthene 1.4 

Unidentified  oils  in  range  of  acenaphthene i  .o 

Fiuorene 1.6 

Unidentified  oils  in  range  of  fluorene 1,2, 

Anthracene  oil: 

Phenanthrene 4.0 

Anthracene i .  i 

Carbazol  and  kindred  nonbasic  nitrogen-containing  bodies 2.3 

Unidentified  oils  in  range  of  anthracene 5.4 

Phenol 0.7 

Phenol  homologues  (largely  cresols  and  xylenols) 1.5 

Tar  bases  (mostly  pyridine,  picolines,  lutidines,  quinolines  and  acri- 

dine) 2,3 

Yellow  solids  of  pitch  oils 0.6 

Pitch  greases * 6.4 

Resinous  bodies 5,3 

Pitch  (460°  F.  fusing-point) f 44. 7 

Total 100. o 


XVII  PRODUCTION  OF  BLAST-FURNACE  COAL  TAR  347 

Production  of  Blast-furnace  Coal  Tar.6  Most  blast-furnaces  in 
the  United  States  employ  coke  as  fuel  and  a  few  use  anthracite 
coal.  Since  all  the  volatile  constituents  have  been  removed  from 
coke,  and  as  anthracite  coal  contains  only  a  very  small  percentage, 
no  tar  is  obtained  when  either  of  these  is  used  for  smelting  ores  in 
blast-furnaces.  In  such  cases  the  gases  evolved  are  subjected  to  a 
purification  process  merely  to  remove  the  entrained  dust,  before 
using  them  for  heating  purposes. 

Owing  to  the  scarcity  of  anthracite  and  the  high  cost  of  bitumi- 
nous coal  in  Europe  and  Great  Britain,  there  is  a  tendency  to  reduce 
the  operating  expenses  by  using  the  latter  in  its  raw  state,  without 
first  converting  it  into  coke.  A  non-coking  bituminous  coal  must  be 
selected  for  this  purpose.  In  such  cases  the  gases  emanating  from 
the  blast-furnace  carry  a  certain  amount  of  tar,  derived  from  the 
volatile  constituents  of  the  coal,  which  must  be  removed  before  they 
can  be  used  for  heating  or  power  purposes.  The  gases  also  carry  a 
comparatively  large  amount  of  dust  derived  from  the  ores  in  the 
blast  furnace,  of  which  a  good  portion  is  removed  by  passing  the 
hot  gases  through  a  device  known  as  a  udry  dust-catcher/1 

Methods  of  Recovery.  After  being  dry-cleaned,  the  gases  are 
subjected  to  a  wet-cleaning  and  cooling  process  by  passing  them 
through  coolers,  scrubbers,  or  washers.  The  centrifugal  washer  is 
usually  preferred  as  it  operates  rapidly  and  economically.  A  part 
o/  the  tar  condenses  in  the  coolers,  and  the  balance  in  the  scrub- 
bers and  washers.  ,  It  carries  a  large  quantity  of  the  wash  water, 
which  may  be  separated. 

Approximately  7  gal.  of  blast-furnace  tar  and  29  Ib.  of  ammo- 
nium sulfate  are  obtained  from  each  ton  of  bituminous  coal  fed  into 
the  blast-furnace.  It  appears  that  the  iron  ore  and  other  minerals 
introduced  with  the  coal,  influence  the  yield  of  tar.  Thus  the  same 
bituminous  coal  gave  the  following  weights  of  tar  per  ton  under 
varying  conditions: 

Distilled  alone  in  gas  works 114  Ib.  of  tar 

Distilled  with  English  iron  ore 66  Ib.  of  tar 

Distilled  with  sand 170  Ib.  of  tar 

The  tar  derived  from  blast-furnaces  always  carries  a  substantial 
proportion  of  mineral  matter,  which  the  dust-catchers  fail  to  re- 


348  COAL  fAR  AND  COAL-TAR  flTCH  XVII 

move,  and  which  serves  to  distinguish  it  from  the  other  varieties  of 
coal  tar. 

Blast-furnace  coal  tar  on  distillation  yields  a  greenish-brown 
creosote  of  low  viscosity,  with  30-35  per  cent  phenolic  content,  also 
a  pitch  of  rather  paraffinoid  character.  A  typical  tar  tests  as  fol- 
lows: specific  gravity  at  60/60°  F.,  1.151;  water  by  volume,  0*2 
per  cent;  phenols  in  tar,  14.6  per  cent;  bases  in  tar,  2.5  per  cent; 
pitch  at  315°  C.,  56.6  per  cent  of  medium  hardness  and  paraffinoid 
character;  and  distillate  to  315°  C.,  43,4  per  cent,  having  a  specific 
gravity  at  60/60°  F.  of  0.980;  naphthalene  little  to  none;  and  min- 
eral matter  13.0  per  cent 

Production  of  Producer-gas  Coal  Tar.6  Unless  the  producer- 
gas  plants  are  of  a  large  capacity  (above  4000  horse-power)  it  does 
riot  pay  to  recover  the  by-products.  The  smaller  producers  are 
designed  to  decompose  the  tar  vapors  and  convert  them  into  per- 
manent gases,  to  avoid  the  expense  of  operating  a  tar-separating 
plant  on  one  hand,  or  the  trouble  occasioned  by  the  tar  clogging  the 
pipes  and  valves  on  the  other.  In  plants  where  the  producer  gas  is 
used  without  separating  the  tar,  it  is  necessary  to  shut  down  about 
one  day  a  week  to  clean  out  the  gas  lines.  In  spite  of  this,  it  is 
only  in  tin-plate  plants,  where  particularly  clean  gas  is  required,  that 
the  practice  is  followed  of  scrubbing  the  producer  gas  to  remove  the 
tar.  Of  the  larger  installations,  the  Mond  by-product  gas  producer 
is  virtually  the  only  one  which  is  designed  to  recover  the  tar  and 
ammonium  sulfate.  Upon  operating  this  type  of  producer  at  low 
temperatures,  as  high  as  150  Ib.  of  water-free  tar  is  recovered  per 
ton  of  coal,  consisting  of  paraffins,  olefines  and  naphthalenes,  with 
smaller  quantities  of  aromatic  hydrocarbons  and  phenols. 

Production  of  Low-temperature  Tars.7  Low-temperature  car- 
bonization processes  are  carried  on  at  400  to  700°  C.,  or  an  average 
of  600°  C,  in  layers  about  4  in.  thick.  The  industry  dates  from 
1906,  when  Thomas  Parker  (who  originated  the  term  "coalite") 
patented  a  plant  for  carbonizing  coal  at  low  temperatures.  The 
yields  are  roughly  as  follows  per  ton  of  coal  carbonized: 

(1)  Gas,  3000  to  3500  cu.  ft.  from  externally  heated  retorts, 
or  20,000  to  25,000  cu,  ft  from  internally  heated  retorts. 

(2)  Tar,  20  to  25  gal 


XVII 


PRODUCTION  OF  LOW -TEMPERATURE  COAL  TARS 


349 


(3)  Ammonium  sulfate,  10  to  25  Ib. 

(4)  Coke,  15  cwt. 

Low-temperature  tars  are  of  a  liquid  consistency  and  contain  a 
comparatively  small  quantity  of  free  carbon.  They  consist  of  50 
to  80  per  cent  of  hydrocarbons  and  20  to  50  per  cent  of  tar  acids. 
The  hydrocarbons  are  mainly  paraffins  and  saturated  cyclic  hydro- 
carbons, with  varying  amounts  of  naphthenes  and  unsaturated  hy- 
drocarbons. Benzol,  toluol,  and  other  aromatic  hydrocarbons  are 
entirely  absent,  or  present  only  in  traces.  The  tar  acids  consist 
mostly  of  the  higher  phenols  of  viscous  to  resinous  character,  with 
very  little  true  phenol,  and  comparatively  little  cresol  or  xylenol. 
They  also  contain  but  small  quantities  of  nitrogen  and  sulfur  de- 
rivatives. 

The  type  of  coal  used  exerts  a  greater  influence  upon  the  char- 
acter of  the  tar  than  does  the  particular  mode  of  treatment,  and  in 
general,  much  variation  occurs  in  the  composition  and  character  of 
the  tars  produced  commercially.  The  creosote  oils  derived  from 
low-temperature  tars  are  too  low  in  specific  gravity  to  meet  the 
current  specifications  in  the  United  States.  Less  pitch  is  obtained 
than  with  high-temperature  tars,  and  its  character  is  quite  different, 
and  generally  poorer  in  quality. 

The  following  yields  are  obtained  from  an  average  British  me- 
dium-coking coal,  subjected  to  various  carbonizing  temperatures, 
expressed  in  percentage  by  weight  of  the  moisture-free  coal : 


400°C. 

45oeC. 

joo'C. 

55o°C. 

6oo°C. 

65o°C. 

7oo°C. 

Tar  (per  cent)  

l.o 

5.62 

7.06 

8.00 

7.60 

6.00 

6.24 

Tar  (gal*  per  ton)    

9.  i 

12.8 

16.0 

17.6? 

l6.4 

14.15 

12.  O 

Tar  (specific  gravity  at  60°  F.)  
Aqueous  distillate  (per  cent)  *  . 

0.958 

5.6 

0,980 

7.OI 

0.986 

7.02 

1.015 

7.70 

1.039 

8.12 

1.078 
8.  20 

1.  080 
7.18 

Gas  (per  cent)                      

2.2 

3.  12 

4.  O< 

7.  14 

Q.IO 

IO.54 

14.  $8 

Coke  (per  cent)  .          

88  2 

8l.7< 

80.  <o 

77.OO 

75.00 

71.00 

7I.OO 

Loss  (per  cent)  

O.I 

O.1O 

O.47 

0.16 

0.18 

0.16 

I.OO 

Pitch  (per  cent  in  tar)              ,..,.,.», 

22.2 

28.8 

27.  ± 

11.4 

14.6 

41.0 

52.  I 

Pitch  (fusing-point  degrees  C.)  

41.2 

17.  0 

52.2 

64.5 

go.5 

01.  C 

95.8 

Pitch  (specific  gravity  at  60°  F.)  ....... 

1.  11 

1.  12 

1.  14 

1.  17 

1.21 

1,25 

1.  20 

Pitch  (free  carbon  per  cent)  .  

14..  2 

<,  1 

4.6 

11.  0 

28.1 

26.8 

25.1 

In  Germany,  low-temperature  tar  is  termed  "Urteer,"  and  in 
Great  Britain  it  is  known  under  various  names,  such  as  "coalite 


350  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

tar,"  "carbocoal  tar,"  "Mond  tar,"  "Delmonte  tar,"  etc.,  depend- 
ing upon  the  particular  type  of  apparatus  in  which  it  is  produced. 

The  reader  is  referred  to  other  sources  for  a  complete  descrip- 
tion of  the  numerous  types  of  retorts  which  have  been  devised  for 
the  low-temperature  process  of  carbonizing  coal. 

Properties  of  Coal  Tars.  As  stated  previously,  the  expression 
"coal  tar"  is  properly  applied  to  tars  derived  directly  from  coal 
without  admixture  of  petroleum.  Coal  tars  differ  in  their  physical 
properties,  depending  upon  their  method  of  production.  The  fol- 
lowing types  are  distinguished: 

( i )   Gas-works  coal  tar 

(a)  Horizontal  retorts 

(b)  Inclined  retorts 

(c)  Vertical  retorts 
Coke-oven  coal  tar 
Blast-furnace  coal  tar 
Gas-producer  coal  tar 

(5)   Low-temperature  coal  tar. 

The  figures  in  Table  XXIII  will  give  a  general  idea  of  the 
physical  properties  of  the  main  types  of  coal  tar  in  their  dehydrated 
state  : 

The  following  colorimetric  test  may  be  used  to  detect  low-tem- 
perature tars:  on  shaking  1-2  ml.  of  the  oily  distillate  with  5  ml. 
aqueous  ferric  oxalate  or  ferric  citrate,  the  aqueous  layer  will  as- 
sume a  dark  blue  coloration,  which  will  turn  a  lemon-yellow  upon 
acidifying  with  N/io  sulfuric  acid  and  then  regain  its  blue  tint  on 
neutralization,  but  turns  purple  and  then  bright  red  upon  adding  an 
excess  of  alkali.  High-temperature  tar  oils  will  not  give  this 
reaction.3 

Methods  of  Dehydrating  Coal  Tar.  It  is  customary  to  dehy- 
drate coal  tars  at  their  point  of  production,  to  avoid  paying  freight 
charges  on  the  water  content.  Provision  is  usually  made  for  the 
gravity  -separation  in  storage  tanks  of  as  much  water  as  possible, 
but  the  amount  that  may  be  removed  in  this  manner  varies  in  the 
case  of  different  tars,  their  mode  of  production,  and  other  factors. 
With  high-temperature  coal  tars  the  settled  product  is  In  the  nature 
of  an  emulsion,  with  the  water  as  the  disperse  phase.  The  amount 
of  water  held  in  stable  suspension  is  greater  in  the  ca&  of  horizontal 


XVII 


PROPERTIES  OF  COAL  TAR 


351 


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352 


COAL  TAR  AND  COAL-TAR  PITCH 


XVII 


gas-retort  tar  than  in  coke-oven  and  vertical  gas-retort  tar,  and  still 
less  with  water-gas  tar,  ranging  from  3  to  10  per  cent  in  the  case  of 
the  first  named,  down  to  i  to  2  per  cent  in  the  last  Sometimes,  the 
emulsion  is  of  a  different  nature,  in  which  the  tar  forms  the  disperse 
phase  and  the  water  content  ranges  from  15  to  70  per  cent.  Such 
emulsions  are  most  difficult  to  break  up  by  the  usual  means  of  set- 
tling, even  at  high  temperatures.  They  may,  however,  be  treated 
by  a  partial  distillation,  as  will  be  described  later. 

Dehydration  may  simply  imply  the  removal  of  the  bulk  of  the 
water  from  a  tar,  so  as  to  render  it  suitable  for  distillation,  or  as  is 
the  case  in  Great  Britain,  it  may  include  the  removal  of  the  light 
oils  as  well,  resulting  in  the  production  of  a  refined  tar  suitable  for 
road  purposes  or  other  uses. 

The  following  methods  have  been  used  for  dehydrating  tars: 

(i)  Settling.  When  the  tar  is  allowed  to  settle  in  storage 
tanks,  the  water  rises  to  the  surface,  where  it  is  drawn  off  through  a 
series  of  outlet  pipes  in  the  side.  This  process  may  be  facilitated,' 

? articularly  in  the  case  of  viscous  tars,  by  heating  to  about  200°  F. 
y  means  of  steam  coils  in  the  bottom  of  the  tank,  supplied  with 
exhaust  steam  from  other  plant  operations.  Many  variations  of 
simple  settling  have  been  suggested,  but  at  best  they  remove  but  a 
portion  of  the  water,  and  are  generally  supplanted  by  one  of  the 
methods  which  follow* 

(2)'  Use  of  Centrifuges.  This  method  has  been  used  with 
more  or  less  success  abroad,  and  only  in  the  case  of  tars  with  tars  of 
low  free-carbon  content,  so  as  to  avoid  the  necessity  of  frequent 
cleaning.  The  tar  is  first  heated  to  a  temperature  of  40  to  50°  C. 

and  run  into  the  rapidly  revolving 
drum  of  a  centrifugal  separator, 
illustrated  in  Fig.  106.  The  tar 
being  heavier  than  the  water  is 
forced  to  the  periphery,  the  water 
forming  a  cylindrical  layer  inside. 
An  annular  diaphragm  A  attached 
to  the  upper  part  of  the  centrifugal 
has  a  ring  or  perforations  where  it 
comes  in  contact  with  the  drum  at 
B.  The  crude  tar  is  introduced 
through  thepipe  C  below  the  dia- 

FIG.  106.— Centrifugal  Tar  Dehydrator*      phragm.       The    speed   with    which 

the  drum  revolves  causes  the  tar 
to  flow  through  the  perforations  into  the  upper  portion  of  the  cen- 


XVII  METHODS  OF  DEHYDRATING  COAL  TAR  353 

trifugal,  where  it  is  removed  through  the  pipe  D.  The  water  is 
drawn  off  through  E  below  the  diaphragm,  which  bars  its  passage 
into  the  upper  section.  This  method  is  particularly  suited  for  treat- 
ing tars  having  approximately  the  same  specific  gravity  as  water,  as 
for  example  water-gas  tar.  The  centrifugal  is  revolved  at  a  speed 
between  2000  and  3000  r.p.m.  Tars  containing  between  30  and 
90  per  cent  of  water  will  have  the  percentage  reduced  to  less  than 
i  per  cent  in  one  treatment.  A  large  portion  of  the  free  carbon 
contained  in  the  tars  is  also  removed,  and  affixes  itself  to  the  inner 
walls  of  the  drum  from  which  it  must  be  scraped  occasionally. 

( 3 )  Horizontal  Stills.    These  are  used  to  a  considerable  extent 
in  Great  Britain  according  to  the  continuous  dehydrating  methods 
proposed  by  Hird,  Chambers  and  Hammond.9    They  depend  upon 
the  use  of  a  horizontal  still  heated  by  tubes  at  the  bottom,  through 
which  the  furnace  gases  are  passed.    The  tar  to  be  dehydrated  is 
caused  to  flow  through  the  still  to  a  depth  of  about  6  in.  over  the 
tops  of  the  heating  tubes,  and  a  heat-exchanger  is  used  on  the  incont* 
ing  wet  tar  and  the  outgoing^  hot  dry  tar,  so  as  to  preheat  the  for- 
mer.   Two  or  several  stills  in  series  may  be  employed,  depending 
upon  the  amount  of  water  carried  by  the  tar  and  the  tonnage  to  be 
treated  per  day. 

(4)  Tube  Heaters.    This  process  has  been  devised  by  T.  O. 
Wilton,10  and  has  met  with  favor  in  Great  Britain.     The  tar  is 
treated  continuously  upon  being  heated  to  170  to  190°  C.  under  a 
pressure  of  30  to  50  Ib.  per  sq.  in.,  by  pumping  through  a  coil  of 
pipes  in  a  furnace  heated  with  coke.    It  is  then  released  into  a  vapor 
chamber  at  atmospheric  pressure,  whereupon  the  water  and  light 
oils  evaporate,  since  they  are  maintained  at  a  temperature  consider- 
ably higher  than  their  boiling  points.     This  is  accompanied  by 
copious  frothing,  due  to  the  fact  that  each  volume  of  water  is 
converted  into  1640  volumes  of  steam.    As  this  method  involves  the 
charging  of  hot  tar  to  the  tube  heater,  no  heat  exchanger  is  used. 

(5)  Cascade  System.     In  Great  Britain,  this  system  has  been 
patented  by  William  Blakeley,11  who  allows  the  heated  tar  to  flow 
over  a  series  of  trays  arranged  in  a  casing,  the  trays  being  intercon- 
nected by  pipes  which  also  serve  to  support  them.    The  tar  is  intro- 
duced in  the  top  tray  and  is  allowed  to  flow  from  tray  to  tray,  while 
the  steam  or  other  heating  medium  is  introduced  in  the  pipes  at  the 
bottom  tray,  and  is  conducted  from  tray  to  tray  upwards.    A  devel- 
opment of  this  process  has  been  used  successfully  in  the  United 
States  in  a  cascade  dehydrator,  consisting  of  a  rectangular  steel 
chamber  enclosing  a  series  of  steel  pans  fitted  with  steam  coils.12 
The  pans  are  set  at  an  incline  writh  alternate  pans  sloping  in  oppo- 
site directions,  so  as  to  form  a  cascade.    Pumps  are  provided  for 
handling  the  crude  and  dehydrated  tar,  also  the  distillate.    The  tar 


354  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

is  introduced  through  a  manifold  at  the  top  of  the  casing  wKich 
delivers  it  to  a  distributing  box  over  the  top  pan,  whence  it  over- 
flows from  pan  to  pan  and  leaves  the  bottom  of  the  casing  free  from 
water*  The  vapors  are  conducted  to  a  combination  vapor-condenser 
and  tar-preheater  whence  they  are  condensed  by  the  raw  tar  on  its 
way  to  the  distributing  box.  A  second  water-cooled  condenser  is 
provided  as  a  safeguard.  The  distillate  is  withdrawn  from  the 
second  condenser  by  a  vacuum  pump,  which  serves  to  maintain  a 
vacuum  of  3  to  4  in.  of  mercury  on  the  casing.  The  dehydrator  is 
operated  so  that  the  exit  tar  attains  a  temperature  of  275  to 
285°  F.,  which  assures  its  complete  dehydration.  A  sufficient  pres- 
sure is  applied  to  the  tar  before  entering  the  casing  to  prevent  the 
evolution/  of  vapors,  this  particular  feature  being  similar  to  the 
Wilton  system.  A  dehydrating  unit  of  this  type  handles  37,000  gal. 
of  gas-works  coal  tar  in  twenty-four  hours,  reducing  the  water  con- 
tent from  7.7  per  cent  to  o.i  per  cent;  likewise  60,000  gal.  of  tar 
containing  4  per  cent  water,  and  100,000  gal.  containing  1.8  per 
cent  water;  in  both  of  the  latter  instances  reducing  the  water  con- 
tent to  o.i  per  cent 

Methods  of  Distilling  Coal  Tar.18  Coal  tar  is  transported  from 
the  gas-works  or  coke-ovens  in  cylindrical  steel  tank-cars  7  to  8  ft. 
in  diameter  and  28  to  30  ft.  long  holding  about  10,000  gal.,  pro- 
vided with  a  dome  on  top  and  heating  coils  inside  for  the  introduc- 
tion of  steam  in  cold  weather  to  reduce  the  fluidity.  It  is  transported 
by  water  in  tank-vessels  constructed  similarly  to  those  used  for  pe- 
troleum, holding  up  to  300,000  gal.  At  the  distilling  plant,  the  tar 
is  generally  stored  in  covered  vertical  cylindrical  steel  tanks  larger 
in  diameter  than  height,  having  a  capacity  up  to  2  million  gallons. 
A  certain  amount  of  water  separates  during  storage  which  is  tapped 
.through  pet-cocks  in  the  side.  Less  often  the  tar  is  stored  in  rectan- 
gular reinforced  concrete  tanks  built  underground. 

Tar  when  heated  to  a  temperature,  usually  in  the  neighborhood 
of  700°  F.,  will  crack  and  decompose,  giving  off  permanent  gas  with 
the  formation  of  insoluble  matter,  known  as  "free  carbon."  This 
reaction  increases  in  velocity  as  the  temperature  increases,  and 
varies  of  course  with  different  tars.  The  effect  of  this  reaction  is  a 
smaller  yield  of  distillate  to  a  given  consistency  of  pitch  residue,  or 
in  other  words,  it  means  that  the  pitch  is  produced  at  the  expense 
o£  the  yield  of  oils.  Since  the  oil  is  the  more  valuable  product,  the 
cracking  is  regarded  as  undesirable.  The  amount  of  cracking  is  a 


XVII  METHODS  OF  DISTILLING  'COAL  TAR  355 

function  of  both  temperature  and  time,  increasing  directly  with 
either  of  these  factors.  The  ideal  system  of  tar  distillation  may  be 
regarded  as  one  which  exposes  the  tar  to  the  lowest  temperature  for 
the  shortest  possible  time  necessary  to  obtain  the  desired  product. 
The  practical  effect  of  these  factors  may  be  exemplified  by  some 
results  on  a  coke-oven  tar  run  to  a  pitch  of  300°  fusing-point  A 
reduction  in  the  time  of  heating  from  twelve  to  one  and  one-half 
hours  resulted  in  an  increase  of  16  per  cent  in  the  yield  of  oils  and 
a  corresponding  decrease  in  the  amount  of  pitch.  Similarly,  where 
the  time  was  kept  constant,  a  lowering  of  the  final  still  temperature 
by  200°  F.  accomplished  approximately  the  same  result.  Greater 
yields  of  oil  may  be  obtained  by  decreasing  both  the  time  and  tem- 
perature, although  the  effects  are  not  necessarily  additive. 

One  method  consists  in  increasing  the  still  heating  surface,  so  as 
to  increase  the  heat  input  in  a  given  time,  and  this  leads  to  the 
continuous  tube-still  of  one  type  or  another,  where  the  time  factor 
is  reduced  materially  over  the  batch  stills.  Another  method  is  to 
reduce  the  still  temperature  by  lowering  the  vapor  pressure  of  the 
oils  through  the  use  of  steam,  vacuum,  or  inert  gases,  as  will  be 
described  presently. 

The  following  methods  have  been  used  for  distilling  coal  tars : 

( i )  Simple  Batch  Stills.  The  first  stills  used  in  the  tar  industry 
in  Europe^were  constructed  in  the  form  of  a  "pot"  or  verticaf  still 
having  a  concave  bottom,  as  illustrated  in  Fig.  107,  where  i  repre- 
sents the  manhole;  2,  safety-valve  connection;  3,  swan  neck;  4,  swan 
neck  stool;  5,  dipping  tap;  6,  steam  inlet;  7,  steam  pipe;  8,  tar  inlet; 
n,  tar  outlet.  The  concave  bottom  is  claimed  to  have  the  advan* 
tages  of  providing  a  larger  heating  surface,  also  to  assist  in  draining 
off  the  pitch  and  to  accommodate  the  expansion  and  contraction  of 
the  metal  plates  without  setting  up  dangerous  strains.  Steam  is 
introduced  during  the  process  of  distillation  through  a  perforated 
pipe  (9—10)  at  the  bottom  and  serves  to  carry  off  the  vapors  more 
rapidly,  also  reduce  the  time  of  distillation.  English  stills  hold  20 
to  40  tons  (4000  to  6000  gal.)  of  tar,  and  are  mounted  on  suitable 
brick  settings  adapted  for  direct  heating  with  coal  or  producer  gas. 

The  vapors  leave  the  still  through  a  large  pipe  connected  with 
the  condenser  coils  immersed  in  water  in  a  rectangular  tank.  These 
coils  are  constructed  of  pipes  ranging  from  6  in.  down  to  3  in^in 
diameter.  The  distillate  is  run  into  small  measuring  tanks  which 
in  turn  empty  into  large  storage  tanks.  Each  fraction  is  caught 


356 


COAL,  TAR  AND  COAL-TAR  PITCH 


XVII 


6. 


separately,  four  fractions  all  told  being  recovered,  viz.:  light  oil  or 
crude  naphtha,  middle  or  carbolic  oil,  heavy  or  creosote  oil  and 
anthracene  oil. 

In  the  United  States  the  customary  form  of  batch  still  consists 
of  a  horizontal  cylinder  with  convex  ends,  heated  directly  with  oil, 
coal  or  gas,  constructed  to  hold  in  the  neighborhood  of  50  tons 

(10,000  gal.)  tar.  Such  stills 
are  about  9  ft  in  diameter  by  20 
ft.  long,  and  about  half  the 
diameter,  or  500  sq.  ft,  is  avail- 
able as  heating  surface.  They 
take  ten  to  twenty  hours  to  com- 
plete distilling  a  charge  to  a 
pitch,  where  40  to  45  per  cent  of 
oil  is  removed  from  the  tar.  A 
typical  still  is  illustrated  in  Fig. 
1 08.  The  tar  enters  through  a 
pipe  into  the  top  of  the  still,  and 
the  vapors  are  drawn  off  through 
another  pipe  of  large  diameter 
attached  directly  to  the  top  of 
the  still,  at  the  center.  The  stills 
are  not  usually  provided  with 
domes,  as  is  the  case  with  petrol- 
eum stills.  The  outlet  pipe  for 
the  pitch  is  located  at  the  bot- 


From  "Coal  Tar  Distillation," 
by  A,  R.  Warnes. 


FlC. 


107.— Vertical    Still 
Coal  Tar. 


for  Refining 


torn,  together  with  inlet  pipes  for 
steam  or  air  agitation.  The  stills 
are  mounted  on  a  brick  setting  provided  with  a  fire  arch  to  in- 
sure uniform  heating,  and  prolong  the  life  of  the  bottom.  The 
process  is  an  intermittent  one.  After  the  tar  has  been  distilled  to 
the  desired  fusing-point  or  consistency,  the  residue  of  pitch  is  dis- 
charged by  gravity,  pumping  or  blowing  out  with  air, 

In  recent  years  the  batch  stills  have  been  somewhat  improved  by 
the  use  of  internal  flues  to  increase  the  heating  area  and  serve  to 
reduce  the  time  of  distillation,  also  to  minimize  the  carbon  deposi- 
tion. A  modern  installation  is  illustrated  in  Figs.  109  to  113,  con- 
sisting of  two  primary  stills  of  9000  gal.  each  and  three  secondary 
stills  of  8000  gal  each.  The  primary  stills  are  of  the  vertical  type 
and  serve  as  preheaters,  since  they  are  equipped  with  spiral  steel 
flues  through  which  the  gases  from  the  secondary  stills  are  passed, 
as  illustrated  in  Fig.  in.  From  the  primary 'stills  the  heated  tar  is 
run  into  the  secondary  stills,  where  direct  heat  is  applied,  and  the 
bulk  of  the  distillation  takes  place;  these  are  shown  in  Fig*  112. 


XVII 


METHODS  OF  DISTILLING  COAL  TAR 


357 


The  pitch  is  run  from  the  secondary  stills  to  the  pitch  copiers  of 
about  5000-gaL  capacity  each,  which  are  illustrated  in  Fig.  113* 
The  vapors  are  condensed  in  a  vertical  shell-and-coil  type  of  con- 
denser filled  with  water,  which  is  located  directly  below  the  primary 
stills,  from  which  the  distillate  is  run  into  the  storage  tanks. 

Another  arrangement  consists  in  operating  the  batch  still  in 
connection  with  a  dehydrator  of  the  continuous  type,  which  has  the 


of  The  'Barrett  Company. 
FlG.  108.— Horizontal  Still  for  Refining  Coal  Tar. 

advantage  of  conserving  heat  and  also  obviates  the  danger  of  foam- 
ing during  the  distillation  process. 

(2)  Vacuum  Distillation.  Vacuum  of  26  to  28  in.  mercury 
may  be  used  to  advantage  in  connection  with  batch  stills  when  run- 
ning to  a  hard  pitch  of  280-300°  F.  fusing-point  Much  better 
yields  of  oil  are  obtained  (e.g.,  about  10  per  cent  at  a  300°  F. 
fusing-point  pitch)  than  by  distillation  under  atmospheric  pressure, 
and  the  reduction  in  cracking  also  has  the  effect  of  lowering  the  per- 
centage of  free  carbon  in  the  pitch.  In  general,  the  use  of  vacuum 
does  not  materially  influence  the  products  until  a  pitch  of  140°  F. 
fusing-point  is  reached,  but  from  there  on  the  vacuum  has  Decided 
advantages  as  compared  with  ordinary  operations,  although  when 


358 


COAL  TAR  AND  COAL-TAR  PITCH 


XVII 


the  fusing-point  of  the  pitch  reaches  a  fusing-point  of  300°  F.  or 
thereabouts,  a  certain  amount  of  cracking  begins,  accompanied  by 
the  evolution  of  gas,  which  makes  it  impractical  to  maintain  the 


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^ ^Pumped  to  Ammonia  &  £ 

5tomqeby*IOPump 

wi  Oil          Heavy  Ot /s    ^      C///5 

25,OOQ6a/t     25flOQQaL      25tOOOGai    2$0006al, 

O"  O1  O""  0"' 

IW2W        230-270*       270-300'  300'+ 

Pumped  from  Pumped  f/vm  Pympedf/vm  Pumped  from 

AccJankfhru  Rec Jan k  thru  RecJanksihru  Rcclanksthru 

*IQPump  *lOPump          *IIPump  *HPump 


Tar 


SYMBOLS 

------  Oil-230-2700 

--------  0,1-270'-  300* 

-------  OiL300'+ 


FIG.  109,  —  Flow  Diagram  of  Dry  Tar  to  Light  and  Heavy  Oils. 


FIG.  no. — Cross-section  of  Tar  Distillation  Plant 

necessary  degree  of  vacuum.  In  distilling  to  a  pitch  of  220°  F. 
fusing-point,  the  final  still  temperature  is  750°  F.  at  atmospheric 
pressure,  in  comparison  to  570°  F.  when  distilled  under  a  vacuum 


XVII 


METHODS  OF  DISTILLING  COAL  TAR 


359 


of  28  in.  mercury.  In  a  vacuum  distillation  plant,  the  oil  receivers 
must  be  in  parallel,  connected  with  suitable  piping,  so  that  one  may 
be  released  to  empty  it,  without  disturbing  the  vacuum  on  the  rest 
of  the  system. 


. 

K- -  ~  3-(f J 


FIG.  in.— Primary  Tar  Still. 


An  alternate  procedure  consists  in  agitating  the  tar  with  steam, 
using  a  vacuum  of  about  15  in.  of  mercury.  The  following  figures 
were  obtained  on  coke-oven  tars  of  9  per  cent  free  carbon : 


360 


COAL  TAR  AND  COAL-TAR  PITCH 


XVII 


Final  Still 
Temp.0  C. 

Per  Cent  by  Weight 

Pitch  Tests 

Pitch 

Oil 

Air  M.  Pt. 

Free  Carbon 

Atmospheric  

400 
300 

64-3 
55-9 

34-9 
43'  I 

220°  F, 

216°  F. 

35  -3  per  cent 
26.1  per  cent 

Vacuum  of  28-in.  .  .  , 

FIG.   112. — Direct-fire  Secondary  Tar  Still. 

'   In  general,  the  softer  the  pitch  produced,  the  less  will  be  the 
advantage  of  vacuum  distillation. 

Heating  in  a  bath  of  molten  metal  under  vacuum  has  also  been 
suggested.14 

(3)   Steam  Distillation.     The  passage  of  superheated  steam 
through  the  contents  of  the  batch  still  also  serves  to  reduce  the  dis- 


FIG.  113.— Pitch  Cooler. 

tillation  temperature  and  to  minimize  the  cracking,15  but  the  amount 
of  steam  required  is  so  great,  that  its  use  has  not  proven  practicable 
from  the  standpoint  of  cost  and  on  account  of  the  greatly  increased 
condenser  surface  required.  This,  however,  does  not  apply  to  the 
use  of  a  small  amount  of  steam  to  agitate  the  contents  of  the  still, 
where  th$  distillation  takes  place  at  atmospheric  pressure. 

The  effect  of  large  volumes  of  steam  is  indicated  by  the  follow- 


XVII 


METHODS  OF  DISTILLING  COAL  TAR 


361 


ing  figures/8  where  steam  was  passed  at  a  rate  of  o.i  i  cu.  ft.  (cor- 
rected at  77°  F.  to  760  mmj  per  gallon  of  tar  per  minute,  ap- 
plicable to  a  coke-oven  tar  of  8.5  per  cent  free  carbon  content: 


Final  Still 

Per  Cent  by  Weight 

Pitch  Tests 

Temp.  °  C. 

Pitch 

Oil 

Air  M.  Pt. 

Free  Carbon 

Ordinary  distillation. 

413 

57.8 

40.1 

280°  F. 

40.  7  per  cent 

Steam  distillation.  .  . 

340 

47.0 

50.6 

*79°  F. 

28,8  percent 

It  may  be  noted  that  the  steam  consumption  was  such  that  the 
condensed  water  approximately  equaled  the  volume  of  the  "oil" 
recovered  on  distillation. 

(4)  Gas  Re  circulation.  By  circulating  an  inert  gas  such  as 
nitrogen  or  carbon  dioxide  through  the  contents  of  the  regular  batch 
stills  at  the  rate  of  i  to  20  cu.  ft.  per  100  gal.  tar,  per  minute,  the 
vapor  pressure  of  the  oil  vapors  is  lowered,  coupled  with  a  reduc- 
tion of  the  still  temperatures  and  an  increase  in  the  yield  of  distil- 
late.17 This  procedure  merely  involves  the  addition  of  a  gas  recir- 
culation  pump  and  closed  distillate  receivers  to  the  batch-still  equip- 
ment. In  practice,  no  provision  is  made  for  the  inert  gas,  as  the 
system  may  be  filled  with  air  at  the  start,  since  in  a  short  time  the 
oxygen  is  used  up  and  the  recirculation  gas  becomes  nitrogen.  The 
formation  of  free  carbon  is  minimized,  and  the  distillation  may  be 
carried  to  a  much  further  point  without  danger  of  coking  of  the 
still  contents.  Whereas  pitches  of  about  300°  F.  fusing-point  rep- 
resent the  hardest  that  may  be  produced  commercially  by  the  fore- 
going distillation  methods,  with  the  recirculation  method,  pitches  of 
400  to  450°  F.  fusing-point  may  readily  be  obtained,  and  with  a 
correspondingly  greater  yield  of  distillate.  Thus,  with  a  coke-oven 
tar  of  8.5  per -cent  free  carbon  content,  65  per  cent  by  weight  of 
distillate  was  obtained  upon  running  to  a  pitch  of  400°  F.  with  a 
carbon  deposit  in  the  still  no  greater  than  was  the  case  upon  run- 
ning to  a  250°  F.  fusing-point  pitch  by  the  ordinary  method,  with 
only  40  per  cent  distillate. 

A  comparison  of  the  oil  yield  by  the  gas-recirculation  method 
on  the  same  type  of  coke-pven  tars  referred  to  under  the  captions 
"Vacuum  Distillation"  and  uSteam  Distillation,"  is  given  below* 
The  gases  were  recirculated  at  a  rate  of  0.33  cu.  ft  \ corrected  to 
77°  F.  and  760  mm.)  per  gallon  of  tar  per  minute,  in  the  case  of 
CO2,  and  at  the  rate  of  0.40  cu.  ft.  (corrected  to  77°  F*  and  760 
mm.)  per  gallon  of  tar  per  minute,  in  the  case  of  N2:r 


.16 


362 


COAL  TAR  AND  COAL-TAR  PITCH 


XVU 


Final  Still 
Temp.  °  C 

Per  Cent  by  Weight 

Pitch  Tests  * 

Pitch 

Oil 

Air  M.  Pt. 

Free  Carbon 

Atmospheric.  

4i3 
358 
33i 

57.8 
46.9 
46.4 

40.1 
52.6 
52.0 

280°  F. 
277°  F. 
*77°  F. 

40  .  7  per  cent 
29.0  per  cent 
27  .  2  per  cent 

Recirculated  COz  — 
Recirculated  N2  

(c)  Continuous  Stills.  Various  expedients  have  been  pro- 
posed18 to  transform  the  batch  distillation  process  into  a  continuous 
operation,  as  for  example  placing  several  stills  in  series  and  flowing 
the  tar  through  them  consecutively  and  taking  different  fractions 
from  each  still^ allowing  the  pitch  to  flow  from  the  last  in  the  series. 
In  Great  Britain  two  continuous  systems  of  tar  distillation  are  in 
use,  as  devised  by  H.  P.  Hird  and  E.  V.  Chambers  Respectively. 
The  Hird  process  19  involves  the  use  of  four  stills,  three  of  which 
are  connected  in  series,  the  first  two  being  heated  by  internal  flues 
and  the  third  being  arranged  for  the  introduction  of  steam.  The 
fourth  still  is  used  for  the  production  of  pitch.  Separate  condensers 
for  each  still  and  suitable  heat  exchangers  are  provided.  The  first 
still  is  maintained  at  190°  C,  the  second  at  240°  C.,  the  third  at 
325°  C,  (producing  creosote  oil),  and  the  fourth  at  275°  C.  The 
stills  are  provided  with  a  series  of  vertical  baffles  and  the  tar  flows 
through  the  system  in  a  comparatively  thin  layer.  The  Hird  system 
is  only  adapted  to  producing  pitches  ranging  in  fusing-point  up  to 
200°  R 

The  Chambers  process  is  a  modification  of  the  cascade  system 
used  for  dehydrating  tars.  It  involves  the  use  of  two  stills  provided 
with  cascades,  three  condensers  and  one  heat  interchanger.  The 
crude  tar  is  preheated  by  flowing  through  the  heat  interchanger, 
and  then  caused  to  flow  down  the  cascade  in  still  No.  i,  followed 
by  a  return  through  the  bottom  of  the  still  which  is  kept  about  one- 
third  full  of  tar.  The  tar  then  passes  through  the  'still  No.  2  in  a 
similar  manner,  and  finally  into  Still  No.  3  which  is  not  equipped 
with  a  cascade,  where  the  residue  is  distilled  to  pitch  with  the  intro- 
duction of  steam.  Still  No.  i  is  maintained  at  210°  C.  and  pro- 
duces light  oil,  still  No.  2  is  kept  at  260°  C.  and  produces  light  oil 
and  creosote,  still'No.  3  is  kept  at  320°  C.  and  produces  anthracene 
oil  and  a  residue  of  pitch.  It  is  claimed  that  a  plant  of  this  type 
will  successfyilly  handle  a  Mond  or  water-gas  tar  containing  as 
much  as  30  per  cent  of  water. 

(6)  Tube  Stills.  These  operate  on  the  principle  of  heating  the 
tar  by  passing  it  through  a  coil  of  pipe  surrounded  by  the  heating 
medium,  and  then  allowing  the  vaporization  of  the  oils  to  take 


XVII  METHODS  OF  DISTILLING  COAL  TAR  363 

place  in  a  vapor  chamber  at  the  exit  of  the  coil,  thus  handling  the 
tar  continuously. 

In  Great  Britain  the  Wilton  process  20  has  met  with  much  favor, 
and  consists  of  a  modification  of  the  method  described  previously 
for  dehydrating  tar.  The  Wilton  tube-still  for  the  continuous  dis- 
tillation process  consists  of  two  successive  heating  coils  in  series, 
.followed  by  a  cylindrical  still  in  which  superheated  steam  is  intro- 
duced, with  expansion  chambers  in  between  each  unit.  The  first 
coil  heats  the  tar  to  200°  C.  under  a  pressure  of  30  to  50  Ib.  per 
sq.  in.  and  removes  the  light  oils  and  water.  The  second  coil  heats 
the  tar  to  230—300°  C.  and  removes  the  creosote  oil.  The  last 
still  removes  the  anthracene  oil  by  means  of  the  superheated  steam 
at  360°  CM  and  separates  the  pitch. 

Other  types  used  in  Europe  include  the  so-called  "Sadenwas- 
ser"  21  and  "Leinweber"  22  stills,  named  after  the  makers. 

Similar  stills  are  in  use  in  the  United  States  with  very  satisfac- 
tory results.23  They  utilize  a  single  heating  coil  when  running  to 
pitches  of  about  200°  F.  fusing-point,  and  two  heating  coils  when 
running  to  a  300°  F.  pitch,  which  is  about  as  hard  as  can  be  pro- 
duced in  this  type  of  apparatus.  The  crude  tar  is  first  introduced 
as  cooling  means  in  the  various  oil  condensers,  whereby  it  is  heated 
sufficiently,  so  that  when  released  into  an  expansion  chamber,  the 
water  and  light  oils  are  vaporized  and  condensed,  whereupon  the 
dehydrated  tar  is  pumped  through  the  first  heating  coil.  After 
passing  through  the  first  coil,  the  tar  is  sprayed  into  a  second  ex- 
pansion chamber  where  the  creosote  oil  is  taken  off  to  fractional 
condensing  means,  and  the  residual  intermediate  pitch  pumped 
through  a  second  coil  in  the  same  furnace  as  the  first  coil,  but  in  a 
hotter  zone,  and  the  same  process  repeated.  For  the  softer  grades 
of  pitch  the  second  stage  may  be  omitted.  The  use  of  vacuum  in 
the  second  stage  will  serve  to  still  further  reduce  the  operating 
temperatures.24  The  smallest  still  of  this  type  handles  from  30,000 
to  50,000  gal  of  tar  per  day,  depending  upon  the  character  of  the 
tar  and  the  grade  of  pitch  desired,  whereas  the  largest  unit  in  op- 
eration in  the  United  States  has  a  capacity  of  90,000  to  140,000 
gal.  tar  per  day.  The  yield  of  oils  in  such  stills  will  run  10  to  15 
per  cent  better  than  the  ordinary  batch  still  in  producing  pitch  of 
300°  F.  softening-point,  due  entirely  to  a  reduction  in  the  time  of 
heating  to  less  than  one-fifteenth  that  required  in  the  latter.  The 
general  flow  relationship  of  a  well-developed  tube-still  installation  in 
the  United  States  is  shown  in  Fig.  114.  * 

^  Continuous  fractional  condensing  columns  have  been  developed 
which  separate  the  vapors  into  sharper  fractions  than  were  previ- 
ously obtainable^  in  the  batch  stills.  Furthermore,  a  number  of 
closely  cut  fractions  may  be  obtained  simultaneously  and  continu- 


364 


COAL  TAR  AND  COAL-TAR  PITCH 


XVII 


ously  from  the  mixed  tar  vapors,  in  a  properly  designed  and  con- 
structed condensing  column,  including*  the  separation  of  creosote  oil, 
naphthalene  oil,  heavy  oil  and  anthracene  oil. 

(7)  Collector-main  Condensers.  A  process  has  been  devel- 
oped 25  in  the  United  States,  in  which  tars  of  the  desired  consistency 
may  be  separated  directly  in  the  collector-main  of  the  coke-oven,  by 
scrubbing  the  hot  vapors  with  the  preheated  tar,  or  else  with  some, 
of  the  recovered  oils,  yyhich  are  introduced  in  the  form  of  a  spray. 
These  serve  to  remove  the  tarry  matter  from  the  vapors,  which  are 


H.£.C.~  HEAT  EXCHANGE  COMtH$tR3. 

FIG.  114.— Flow  Diagram  of  Continuous  Tube-still  for  Coal  Tar. 

thereby  cooled  and  at  the  same  time  the  gases  are  enriched.  The 
equipment  is  illustrated  diagrammatically  in  Fig.  115. 

The  process  operates  as  follows :  the  hot  gases  from  the  ovens 
pass  up  the  ascension  pipes,  i,  into  the  collector  main,  2,  which  is 
connected  at  one  end  with  the 'foul  gas  or  air-cooled  main  3.  The 
two  mains  have  a  continuous  fall  in  the  direction  of  gas  flow,  and 
tar  is  circulated  through  them  by  the  pump,  4,  and  gravitates  back 
to  the  tank,  5,  accompanied  by  the  heavier  tar  fractions  which  have 
condensed  from  the  gas. 

The  essentially  valuable  feature  of  the  process  is  that  road  tar 
of  any  required  standard  can  be  withdrawn  from  the  air-cooled  or 
foul  gas  mam  at  point  6,  at  which  the  temperature  of  the  gas  is 
stiirabove  the  dew  point  of  the  lighter  tar  constituents,  which  are 
carried  forward  with  the  gas.  By  a  simple  manipulation  of  this 
fundamental  ohvsical  condition  or  the  foul  eas  stream,  road  tar 


XVII       RECOVERY,  TREATMENT  OF  COAL-TAR  DISTILLATES 


365 


may  be  produced,  continuously  or  intermittently,  the  tar  so  ob- 
tained being  superior  in  essential  respects  to  that  produced  by  de* 
hydration  or  distillation  in  stills.  Perfectly  dry  road  tar  may  be 
run  while  hot  from  the  seal  pot,  12,  to  the  receiver,  11,  where  the 
viscosity  is  checked  and  adjusted,  if  necessary,  by  mixing  with  oil 
or  road  tar  of  suitable  consistency. 

With  a  pitch  run  to  300°  F.  fusing-point,  a  70  per  cent  oil  yield 
is  claimed,  as  compared  with  44  per  cent  in  a  batch  still.  Creosote 
oil  as  well  as  hard  pitch  may  be  collected  in  a  similar  manner.  Hard 
pitch  may  be  burnt  as  fuel,  or  returned  to  the  coke-ovens  with  the 
charge  of  coal. 

This  process  represents  quite  a  forward  step,  and  is  rapidly 
being  adopted  in  by-product  coke-ovens,  both  in  the  United  States 


FIG.  115. — Collector-main  Condenser  for  Coal-tar  Distillation, 

and  abroad,  since  it  is  both  more  efficient  and  economical  than  the 
use  of  condensers  and  scrubbers. 

Recovery  and  Treatment  of  Coal-tar  Distillates.  On  refining 
coal  tar  by  any  of  the  distillation  processes  previously  outlined,  one 
or  more  of  the  following  distillates  are  obtained: 

(1 )  Light  Oil.    At  the  commencement  of  the  distillation  proc- 
ess, the  light  oil  or  ucrude  naphtha"  distils  over,  and  comprises  the 
entire  distillate  lighter  than  water,  being  obtained  below  a  vapor 
temperature  of  200°  C,    This  fraction  is  first  washed  with  alkali 
to  remove  the  tar  acids,  and  then  redistilled  and  fractioned  into 
crude  benzol,  toluol,  solvent  naphtha  (xylol)  and  heavy  naphtha. 

(2)  Middle  Oil    This  is  generally  considered  to  include  the 
fraction  boiling  between  200  and  250*  C    In  some  cases  it  is  mi^ed 


366  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

with  the  ensuing  fraction — the  heavy  oil — provided  the  mixture  will 
meet  existing  specifications  for  creosote  oil.  In  other  cases  the 
middle  oil  is  first  extracted  with  caustic  soda  to  remove  the  tar  acids 
before  it  is  mixed  with  the  heavy  oil,  for  use  as  creosote.  Still 
another  alternative  consists  in  redistilling  the  middle,  oil  in  fire- 
heated  stills  to  separate  it  into  the  following  fractions :  crude  naph- 
tha up  to  210°  C,  acid-naphthalene  oil  from  210  to  250°  C,  and 
creosote  oil  above  250°  C.  The  crude  naphtha  is  treated  with 
caustic  soda  to  remove  the  tar  acids  and  then  worked  up  with  the 
light  oil  fractions.  The  acid-naphthalene  oil  is  first  cooled  in  pans 
to  crystallize  out  the  naphthalene,  whereupon  it  may  either  be  mar- 
keted as  such  under  the  designation  "tar-acid  oil,"  according  to  the 
percentage  of  tar  acid  content  (e.g.,  15  per  cent,  25  per  cent,  50 
per  cent,  etc.,  as  the  case  may  be),  or  it  may  have  the  tar  acids 
removed  and  marketed  as  naphthalene  oil. 

In  Germany,  the  practice  consists  in  distilling  the  middle  oil  in 
a  fire-heated  vacuum  column  still,  which  gives  much  closer  boiling 
fractions,  as  follows:  crude  heavy  naphtha  up  to  200°  C.,  a  second 
fraction  from  200  to  220°  C.  containing  the  bulk  of  the  cresylic 
acid  and  comparatively  little  naphthalene,  next  a  closely  cut  naph- 
thalene oil  fraction  carrying  a  high  percentage  of  crude  naphtha- 
lene, leaving  a  residue  of  so-called  creosote  oil. 

The  tar  acids  extracted  from  the  various  fractions  ^  obtained 
principally  from  the  middle  oils  are  obtained  as  their  sodium  salts, 
which  in  turn  are  treated  with  carbon  dioxide  to  liberate  the  tar 
acids,  phenols,  etc.  These  acid  products  are  separated  and  mar- 
keted under  the  following  designations:  phenol,  cresols,  97-^99  per 
cent  straw-colored  cresylic  acid,  95  per  cent  dark  cresylic  acid, 
ortho-cresol,  meta-cresol,  para-cresol,  etc.  They  are  variously  used 
for  the  production  of  emulsifiable  disinfectants,  cattle  sprays,  and 
as  flotation  oils  for  the  concentration  of  certain  grades  of  mineral 
oils. 

(3)  Heavy  Oil.     This  is  variously  known  under  the  terms 
heavy  oil,  creosote  oil  and  dead  oil,  and  may  either  represent  the 
fraction  between  250°  C.  to  the  end  of  the  distillation,  or  the  frac- 
tion between  250°  C.  and  the  anthracene  oil  fraction.     United 
States  practice  consists  primarily  in  adjusting  the  heavy  oil  fraction 
to  meet  the  various  specifications  established  for  creosote  oil  for 
use  in  wood  preservation.26     This  may  be  accomplished  by  con- 
trolling the  distillation  range  of  the  fraction,  or  by  mixing  together 
various  fractions  obtained  from  the  middle  and  heavy  oil  respec- 
tively.   In  either  case,  it  is  advisable  to  remove  any  naphthalene  by 
cooling  and  filtering. 

(4)  Anthracene  Oil    Unless  it  is  intended  to  extract  anthra- 
certfe,  the  anthracene  oil  fraction  is  not  made,  and  the  entire  cut  is 


XVII     RECOVERY  AND  TREATMENT  OF  COAL-TAR  RESIDUALS         367 

worked  up  for  creosote  oil.  Where  it  is  intended  to  produce  an- 
thracene, the  anthracene  oil  fraction  is  cooled  in  pans  or  tanks  until 
the  anthracene  crystallizes  out,  whereupon  it  is  filter-pressed  to 
obtain  a  cake  containing  20—30  per  cent  anthracene,  or  else  sub- 
jected to  a  hot  hydraulic  pressing  to  remove  more  oil  and  produce 
a  cake  containing  30-40  per  cent  anthracene.  The  anthracene  is 
used  principally  to  produce  alizarin  and  other  coal-tar  dyes. 

Recovery  and  Treatment  of  Coal-tar  Residuals.  At  the  close 
of  the  distillation  process  the  residual  product  consists  either  of 
coal-tar  pitch,  or  else  refined  coal  tar,  depending  upon  its  physical 
characteristics.  There  is  no  sharp  line  of  demarcation  between  the 
two,  although,  in  general,  residuals  having  a  fusing-point  above 
80°  F.  (cube  method — Test  15^)  are  known  as  pitches,  whereas 
those  fusing  below  are  considered  refined  coal  tar.  The  charac- 
teristics of  a  given  residual  will  vary  with  the  nature  of  the  tar, 
the  particular  method  of  distillation,  and  the  quantity  of  distillate 
removed.  When  the  distillation  has  been  completed,  the  hot  pitch 
is  run  into  coolers  illustrated  in  Fig.  113,  and  when  the  temperature 
falls  to  250  to  300°  F.  the  product  is  either  run  into  barrels  or  into 
a  large  rectangular  concrete  enclosure  known  as  a  "pitch  bay," 
where  it  is  allowed  to  solidify.  Various  methods  have  been  sug- 
gested to  facilitate  the  handling  of  hard  pitches,27  consisting  in 
molding  it,28  rapidly  cooling  the  pitch  and  breaking  it  into  frag- 
ments,29 comminuting  the  product,30  dropping  the  melted  pitch  from 
an  elevation  into  a  body  of  water,81  forming  an  aqueous  suspension 
with  a  peptizing  agent,82  etc. 

If  the  distillation  is  continued  to  the  desired  point,  then  the 
residue  is  known  as  "straight-run  coal-tar  pitch."  On  the  other 
hand,  if  the  distillation  is  carried  to  a  point  where  the  residue  is 
harder  and  more  infusible  than  desired,  and  is  thereupon  fluxed  to 
the  desired  consistency  and  fusing-point,  either  with  certain  frac- 
tions of  the  distillate  3S  or  a  flux  of  different  origin — usually  of  little 
value  commercially — or  with  other  tars,84  then  the  pitch  is  known 
as  "cut-back  coal-tar  pitch."  S5 

It  has  been  claimed  that  coal-tar  pitch  treated  with  petroleum 
distillate  (e.g.,  naphtha)  and  steam  in  a  heated  vessel  with  agita- 
tion, and  then  being  allowed  to  settle,  will  separate  into  (a)  a 
clear  supernatant  liquid  suitable  for  use  as  a  paint  vehicle,  and  (b) 


368  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

a  pitch-like  mass  suitable  for  the  manufacture  of  roofing  com- 
pounds.86 Processes  have  been  described  in  which  low-temperature 
coal  tar  is  distilled  to  a  pitch  in  the  presence  of  NaOH ;  *r  likewise 
the  steam-distillation  of  coal-tar  pitch  with  Fe203  and  FeCl3  in  com- 
bination with  montan  wax,  whereupon  distillates  are  said  to  be  ob- 
tained composed  of  waxy  and  resinous  products.88 

The  crystallization* of  naphthalene,  anthracene,  phenanthrene, 
etc.,  from  coal  tars  and  their  distillates  may  be  inhibited  by  adding 
a  small  percentage  of  stearyl  chloride.89 

Coal-tar  residuals  have  found  many  uses  in  the  arts,  among 
which  may  be  cited  the  following:  very  soft  pitches  and  refined 
coal  tars  are  used  for  saturating  felts ;  for  dust-laying  purposes  on 
roads  and  pavements;  as  the  base  of  various  kinds  of  paints  and 
protective  coatings  for  metals,  masonry,  and  other  structural  ma- 
terials. Moderately  soft  pitches  having  a  fusing-point  between  80 
and  120°  F.  are  used  principally  for  road  binders  and  sometimes 
for  waterproofing  work.  Medium  hard  pitches  having  a  fusing- 
point  between  120  and  160°  F.  are  used  for  constructing  "pitch- 
and-felt  roofs";  for  laminated  membranes  used  in  waterproofing 
foundations  of  buildings,  tunnels,  subways  and  bridges;  as  pipe- 
dips  ;  as  a  binder  in  constructing  bituminous  concrete  and  macadam 
pavements;  for  filling  the  joints  in  block  pavements;  and  for  manu- 
facturing the  better  grades  of  bituminous  paints.  Hard  pitches 
having  a  fusing-point  between  160  and  212°  F.  are  used  principally 
as  a  binder  for  fuel  briquettes.  Very  hard  pitches  having  a  fusing- 
point  above  212°  F.  are  employed  as  a  binder  for  sand-cores  in 
forming  castings  of  iron  and  steel;  for  manufacturing  electric-light 
carbons,  battery  carbons,  carbon  brushes  for  motors  and  dynamos, 
black  "day  pigeons"  for  target  shooting,  and  sundry  plastic  com- 
positions for  insulating  purposes,  as  a  filler  for  rubber  goods,40  etc* 
It  has  been  pointed  out41  that  very  hard  coal-tar  pitches  (fusing- 
point  between  300  and  400°  F.)  may  be  cut-back  upon  melting  with 
pitches  of  a  lower  fusing-point. 

Coal-tar  pitches  are  remarkably  resistant  to  the  disintegrative 
action  of  water,  and  are  therefore  well  adapted  for  sub-soil  water- 
proofing. They  are  more  weather  resistant  than  wood-tar  pitch, 
rosin  pitch,  lignite-tar  pitch;  shale-tar  pitch  and  bone-tar  pitch,  but 


XVII     RXCOrERY  AND  TREATMENT  OF  COAL-TAR  RESIDUALS        369 

are  Inferior  to  carefully  prepared  residual  asphalts  obtained  from 
jaetroleum,  blown  petroleum  asphalts,  wurtzilite  asphalt,  fatty-acid 
pitches  and  pure  native  asphalts  containing  approximately  the  same 
percentage  of  volatile  matter. 

J  The  manufacture  of  pitch-coke  has  assumed  considerable  irnpor- 
£ance  in  recent  years,  for  use  in  the  metallurgical  industries,  espe- 
cially in  the  production  of  certain  high-grade  castings,  on  account  of 
,fts  extreme  purity  and  freedom  of  deleterious  mineral  constituents 
Whkh  are  present  in  coke  produced  directly  from  coal,  also^  for 
manufacturing  electrodes.  Pitch-coke  results  when  coal-tar  pitch 
fc  distilled  in  a  retort  until  ail  the  volatile  ingredients  have  been 
Driven  off.  As  the  distillation  proceeds  beyond  the  anthracene  oil, 
the  character  of  the  distillate  assumes  a  grease-like  consistency, 
\vhich  thickens  as  the  distillation  proceeds.  At  the  same-  time  a 
strong  evolution  of  gas  (mainly  hydrogen)  takes  place,  accom- 
panied with  a  certain  amount  of  ammoniacal  liquor.  The  residue 
at  this  stage  is  very  pasty  and  of  a  high  fusing-point  and  there  is 
Considerable  danger  of  the  still  foaming  over.  As  the  heating  is 
continued,  the  mass  cokes  and  the  distillate  appears  as  a  transpar- 
ent ruby-red  resinous  substance,  having  a  specific  gravity  above  1.22, 
known  as  "pitch  resin,"  which  melts  between  40  and  100°  C.4*  The 
temperature  at  the  close  of  the  distillation  ranges  between  800  and 
1000°  F.  .  The  yield  of  resin  may  be  increased  by  distilling  the 
pitch  with  steam  in  the  presence  of  Fe2O8  and  FeCX48  Another 
type  of  pitch  resin  (fusing-point  105-110°  C)  may  be  obtained 
fft>m  the  sludge  produced  in  refining  the  light  oils  with  sulfuric 
a$id,  which  is  neutralized  with  caustic  soda  and  distilled  to  225- 
300°  C,  under  a  vacuum  of  28  in.44  The  character  of  the  pitch- 
coke  varies,  depending  upon  the  type  of  apparatus  in  which  the 
pitch  is  coked,  the  time  of  heating,  and  the  final  temperature  at- 
t^ined.  It  consists  of  practically  pure  carbon,  except  for  0.2  to 
0.5  per  cent  ash.  In  Europe  the  distillation  is  performed  in 
special  cast-iron  pot  stills  with  large  doors  or  man-holes  to  facili- 
t$te  cleaning,  holding  i  to  2J4  tons  of  pitch,  which  are  run  on  a 
thirty-six  hour  cycle.  The  resulting  coke  is  quenched  with  water 
and  then  chopped  out  of  the  still  by  hand.  The  pitch  charged 
ifsually  has  a  fusing-point  of  60  to  75°  C.,  and  the  products  ob- 


37$  COAL  TAR  AND  COA&TAR  WZTJEf  ^  . 

,      .  *  •    *      '  '        '  '  $   * 

tamed  include  30  to  40  per  cent  of  aa  0range<plored  waxy  grft*s? 
(specific  gravity  1.14  to  1.22);  4  to  6  per  cent  of  pitch-resin^ 
traces  of  aimmonia;  and  56  to  60  percent  of  pitch-coke.  :'  '* 

In  the  United  States  a  large  quantity  of  pitch-coke  has^b^eh 
produced  by  first  preparing  d  pitch  having  a  fusing-point  of  400  t§ 
450°  F.  by  the  recirculation  method  of  distillation,45  which  is  therj 
coked  in  a  bee-hive  type'of  coking  oven,46  no  attempt*being  rrfadfe 
to. recover  the  by-products  which  are  employed  to  furnish  the  hea^ 
required  for  the  coking  operation.  The  pitch  used  has  a  fusing? 
point  (cube  method — Test  i$c)  of  440°  F.  and  fixed  carbon  (Teit 
19)  63  per  cent.  A  charge  of  6.5  tons  may  be  coked  in  sixty-foil^ 
hours  at  a  maximum  temperattire  of  1100°  F.  The  coke  is  the^ 
quenched  with  water  and  removed,  whereupon  it  contains  i  pe¥ 
cent  of  volatile  constituents,  0.48  per  cent  ash  and  0.38  per  cent 
sulfur,  being,  approximately  98  per  cent  pure  carbon.  The  usual 
unit  is  a  5000  gal.  still  with  a  4000  to  4500  gal.  charge,  operating 
on  a  48  hour  cycle,  yielding  60  to  75  per  cent  oil  from  coke-oven 
tars,  A  modified  type  of  pot-still  is  also  used,  consisting  of  a  cyliri* 
drical  still  set  horizontally  in  brickwork,  so  that  its  entire  circum* 
ference  is  surrounded  by  the  hot  gases,  thereby  preventing  con- 
densation and  speeding  the  distillation  process.47  Alternate  pro- 
cedures consist  in  distilling  in  vacuo;  mixing  the  pitch  with  coke 
breeze  and  charging  same  into'the  coke  ovens;45  spraying  the  melted 
pitch  with  steam  into  the  coke-oven  chamber  ;40  etc.  A  cellular  pitch 
coke  suitable  for  use  as  a  decolorizing  agent  may  be  obtained  by 
distilling  coal-tar  pitch  with  NaOH,  KOH,  MgO,  or  CaO.50  * 

The  successful  coking  of  pitch  has  provided  the  necessary  oi#- 
let  for  the  surplus  production,  which  cannot  be  disposed  of  through 
the  regular  channels. 

Table  XXIV  gives  a  schematic  outline  of  the  various  products 
derived  from  coal  upon  distilling  it  destructively,  including  the 
commercial  substances  produced  from  coal  tar,  as  practiced  in  the 
United  States. 

Properties  of  Coal-tar  Pitches.  The  figures  in  Table  XXV  will 
serve  to  give  a  general*  idea  of  the  limiting  physical  characteristics 
oi  the  pnhcipal  types  of  coal-tar  pitdht  '  in 

:  Chttrch  and  Wfeiss  examined  representative  Specimens  of  coal- 
tar  pitches,**  with  the  following  results,  in  which  A  represents  gas- 


TABLE  XXIV 

PRODUCTS  DERIVED  FROM  COAL, 


COAL 


.     I  ,  . 

1 

|    .A.    | 

GAS  LIQUOR                              *                                                             1      COKE    | 

1 

1 

1                                1                                 I                                I                                 I                                1                                 1                               1 

II                                    III                              II                    1                    1 

1  D?.Ao"««  1  1   BEN20L  1  1   TOLUOL   1  1   XYLOLS    1  1  SULFUR  ||CVANOGE^|"-1-UM3,NAT.N«!JJ  ryEL  M  | 

|T;;T,ASI  1  £s&»  \  \*T»™™\  K^\\^^^nfo^i\  \'SKS&M  \     fETALcouK\CICAtl  1  °**™™  \  \  TO«TIC  1  tem^l 

II                                                                  •                                      | 

i  „.  

£                  1                                                                 |                       _£ 

iii 

[xANIHATCEjI^^^IJJ                                                                     [sULPOCYANIDEJ    (FenROCYANIDtj                                                                                                                  |  1 

1  1                                                                                                                            |LUBRICANT|  [CRUCIBLE)  [iLECTHooEs| 

j                                                            ;„'.£._.._  -L  -.                                                              T/> 

kR 

r"x||*j]oNJ                                                      f    CYANIDE    |  |FERRICYANIDE|  f~l'''S!§e*N~l 

1              ,                                                                                                                                     1 

1 

I   ...       I 


|,M«^1|   «««««.  ||P*,HT|  |.  OOF,NG||«TMMKW,H.| 

[    HARD 

PITCH   [ 

XVIl 


PROPERTIES  OF  COAL-TAR  PITCHES 


371 


I 


I 


ill 


i  iJ 


•a 

a 


•a 


S; 


;1 


!U* 


•» 


j!3S§, 

B  «j— '  H'~I't!'^'~l  S  $J  StS^-^S  4>  fc*^»^ 

1       Hli 


'^•^©•KSS^Iig  f-a-s     'aff^ifta^ll   Si? 
UBIXIIIIIIiSlI   III     IIIII'I2|J  ||8 


eeeeebbebbbb 


372 


COAL  TAR  AND  COAL-TAR  PITCH 


XVII 


works  coal-tar  pitch  obtained  from  horizontal  retorts,  B  gas-works 
coal-tar  pitch  from  inclined  retorts,  C  gas-works  coal-tar  pitch  from 
vertical  retorts,  D  Otto-Hoffman  coke-oven  coal-tar  pitch,  E  Semet- 
Solvay  coke-oven  coal-tar  pitch,  and  F  Scotch  blast-furnace  coal- 
tar  pitch. 

TABLE  XXVI 


A 

B 

C 

D 

E 

F 

(Test   7)    Sp.gr.  a  t6o°/6o°F... 
(Test   9*)  Hardness  at  u  5°  F  .  .  ,  . 
Hardness  at  77°  F  

1.30 

Too  soft 

19 

1.28 

Too  soft 

4° 

1.19 

Too  soft 
44 

1.25 

Too  soft 
4* 

1.25 

Too  soft 
39 

1.23 

3*4 
41 

Hardness  at  32°  F  
(Test  i$c)  Fusing-point  (cube 
method)0  F  

2 

I2< 

2 
123 

2 
125 

3 
126 

2 
126 

8 
135 

(Test  19)    Fixed  carbon  (per  cent) 
(Test  21)    Sol.    in    carbon    disul- 
fide  (per  cent)  

41-5 
64,9 

37-0 
67.8 

I6.3 
89.5 

28.5 
79*9 

28.2 
82.5 

14.4 
58.2 

Non-mineral        matter 
insoluble  (per  cent). 
Mineral    matter     (per 
cent)  

34-9 

0.2 

32.0 

0.2 

10,3 
0.2 

19.7 
0.4 

17.4 
O.I 

30.0 
11.  8 

(Test  22)    Carbenes  (per  cent)  
(Test  31)    Free  carbon  (per  cent) 

3-5 

34-9 

2.8 
30.8 

"    5-3 
8.0 

7-4 
21.  1 

5-9 
18.3 

2.6 

28.4 

"A  sample  representing  a  well-advertised  brand  of  straight-run 
gas-works  coal-tar  pitch  marketed  for  built-up  roofs  was  tested  by 
the  author  with  the  following  results : 

(Test   7)    Specific  gravity  at  77°  F i.*S 

(Test  9*)  Hardness  at  1 1 5°  F 95 

Hardness  at  77°  F ao 

Hardness  at  32°  F o 

(Test   9*)  Consistency  at  115°  F 5-° 

Consistency  at  77°  F 

.Consistency  at  32°  F 

(Test   9<f)  Susceptibility  index 

(Test  10*)  Ductility  at  115°  F 

Ductility  at  77°  F 

(Test   9^)  Ductility  at  32°  F 

(Test  1 1)    Tensile  strength  at  1 1 5°  F 

Tensile  strength  at  77°  F 4-05 

Tensile  strength  at  3*°  F 8.5 

(Test  15*)  Fusing-point  (cube  method) "*  F, 

(Test  16)    Volatile  matter,  500°  F.  in  5  hrs 8.2  per  cent 

(Test  17*)  Flash-point * 3$o  F, 

The  consistency,  tensile  strength  (multiplied  by  id)  and  duc- 
tility curves  of  this  specimen  are  shown  in  Fig*  116.  * 


24.7 
>  150 

>  IOO 

35 
75-5 
o 

0.15 


XVII 


PROPERTIES  OF  COA^TAR  PITCHES 


373 


Coal-tar  pitches  are  characterized  as  follows:52 

1 )  Jet-black  streak  on  porcelain, 

2)  Carbonaceous  matter  clearly  visible  under  microscope. 
3  )   Comparatively  high  specific  gravity. 

4)  High  susceptibility  index.  This  means  that  they  are 
largely  influenced  by  changes  in  temperature,  becoming  brittle  in 
winter,  and  softening  under  extreme  summer  heat. 


77' 


115° 


140 
ISO 
120 
110 
100 
90 
60 
70 
60 
50 
40 
30 
20 
10 

A 

ll  /" 

N, 

LEGEND 
Hardness 

_•—.  ,   jffgjyfafajQ) 

—  .—  Ductility 

O     Fusing  fVnt 

\i 

\ 
\ 

\ 

i 

\ 

i 

\ 

\ 

r 
i 

\ 

\ 

55 

^ 

{. 

/^ 

*^V 

^ 

S 

\ 

15.5 

\ 

\ 

v 

\ 

\ 

\ 

1. 

\ 

\ 

Jl 

46.5 

\ 

\ 

4 

\ 

\      AOL 

(3 

s 

V 

?< 

^.        \ 

V 

\ 

/ 

s, 

\ 

^ 

ft, 

•hJHB 

^ 

' 

^l. 

F*1! 

t 

rjri-rr 

=233 

BBtaM 

its 

t»«    i 

0      10     20    30     40     SO     60     70     80     90     100     110 

Temperature,  Degrees  Fahrenheit 

FlG.  1 1 6.— Chart  ot  Physical  Characteristics  of  Coal-tar  Pitch* 

(5)  High  ductility  when  tested  at  temperatures  ranging  be- 
tween the  solid  and  fluid  states. 

'6)   Characteristic  odor  on  heating. 

^7)   Pass  rapidly  from  the  solid  to  the  fluid  state. 

[8)   Comparatively  high  percentage   of  volatile  constituents 

i  heated  at  ?oo°  r .  for  five  hours. 


when 


(9)  Comparatively  high  percentage  of  fixed  carbon.     , 

(10)  Comparatively  high  percentage  of  non-mineral  matter  in- 
soluble in  carbon  disulfide  ("free  carbon"). 

N     ( 1 1 )   Comparative  insolubility  in  petroleum  naphtha, 
(12)   Comparatively  small  percentage  of  sulfur. 


374  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

( 13 )  Naphthalene  present  in  most  instances. 

(14)  Solid  paraffins  are   either  absent  or  present  in  small 
amounts. 

£15)   The  sulfonated  constituents  are  soluble  in  water. 

(16)  The  distillate  to  coke  contains  a  comparatively  large 
tmount  of  tar  acids. 

(17)  Give  the  diazo  reaction. 

( 1 8  )  Very  slightly  soluble  in  ethyl  alcohol,  forming  a  yellowish- 
brown  solution,  with  an  intense  greenish-blue  fluorescence. 

Low-temperature  coal-tar  pitches  may  be  differentiated  from 
high-temperature  pitches,  since  the  former: 

contain  more  phenolic  bodies. 

contain  solid  paraffins. 

contain  traces  to  no  naphthalene  and  anthracene. 

Attempts  have  been  made  to  oxidize  coal-tar  pitches  in  the  fol- 
lowing ways :  heating  in  air  with  MnO2  or  HNO3  ;53  heating  in  air 
with  MnO2  and  NH4C1;54  blowing  at  an  elevated  temperature  (e.  g. 
370°  C.)  by  the  same  process  used  for  treating  petroleum  as- 
phalts ;55  blowing  with  air  under  pressure  ;56  blowing  with  air  in  the 
presence  of  sulfur;57  blowing  with  air  in  the  presence  of  sulfur, 
CaO  and  KC1O8;58  blowing  with  air  in  the  presence  of  MeCHO 
and  NHa;59  blowing  with  air  in  the  presence  of  H2SO4;60  blowing 
with  air  in  the  presence  of  H2SO4  and  a  persulf ate  or  perborate ; 61 
blowing  with  air  in  the  presence  of  Fe2O3;62  blowing  with  air  in 
the  presence  of  FeCls  or  Fe2O3  containing  sulfur;68  treating  with 
oxygen  at  an  elevated  temperature  in  the  presence  of  boric,  phos- 
phoric or  hydro-iodic  acid;64  blowing  with  oxygen  in  the  presence 
of  nitrous  oxides;65  first  emulsifying  a  mixture  of  coal-tar  pitch  and 
heavy  tar  oils  with  an  aqueous  solution  of  Na2CO3  and  Na2SiO3  and 
then  adding  BaO2.66  Processes  have  also  been  described  for  blowing 
a  mixture  of  coal-tar  pitch  with  saponified  vegetable  oil,67  or  with 
asphalt  or  lignite-tar  pitch.68 

The  presence  of  comparatively  large  amounts  of  volatile  con- 
stituents results  in  disproportionately  high  losses  in  the  blowing 
operation.  Samples  tested  by  the  author  showed  a  slight  lowering 
of  specific  gravity,  a  decrease  in  the  hardness  for  a  given  fusing- 
point,  a  decrease  in  the  susceptibility  factor  (L  e*,  the  material  was 
less  affected  by  changes  in  temperature)  and  no  appreciable  change 


XVII  PROPERTIES  OF  COAL-TAR  PITCHES  375 

in  the  ductility.  Blown  coal-tar  pitches  have  not  been  marketed, 
nevertheless  they  warrant  further  development. 

Coal-tar  pitches  may  be  vulcanized  by  heating  with  sulfur;69 
or  a  mixture  of  sulfur  and  alum;70  or  a  mixture  of  sulfur  and 
CaOCl2  ;71  or  with  an  alkaline  polysulfide  or  antimony  sulfide  ;72  or 
with  spent  Fe2O3  (obtained  in  the  purification  of  coal  gas)  in  the 
presence  of  FeCl3  or  MnSO4;73  or  with  S2C12  (with  or  without  sul- 
fur)7* or  by  heating  with  H2SO4;75  or  by  heating  with  H2SO4  and 
subsequently  heating  to  a  higher  temperature  until  the  acid  is  de- 
composed;76 or  with  organic  nitro-  or  sulfochloride  derivatives;77 
or  with  SaCla  or  thionylchloride  and  then  combined  with  phenol- 
formaldehyde  resin;78  or  by  treating  a  mixture  of  coal-tar  pitch 
and  vegetable  oil  with  nitric  acid  and  vulcanizing  with  sulfur;79 
or  by  heating  a  mixture  of  coal  tar  and  vegetable  oils  or  fats  with 
H2SO4.80  These  processes  serve  to  raise  the  fusing  point  of  the 
pitch  and  make  the  product  more  resistant  to  temperature  changes. 
In  Germany,  sulfurized  coal-tar  pitch  has  been  marketed  under  the 
name  "Holzzement"  for  cementing  together  layers  of  coal-tar  satu- 
rated felt  in  constructing  built-up  roofs.81 

A  type  of  coal-tar  pitch  suitable  for  use  in  constructing  steep 
built-up  roofs  and  which  will  not  run  or  flow  at  high  sun  tempera- 
tures when  exposed  at  angles  in  excess  of  30°  may  be  prepared  as 
follows:  distilled  coal-tar  pitch  or  coke-oven-tar  pitch  is  heated 
to  550°  F.  and  2  to  3  per  cent  of  ammonium  sulfate  or  zinc  sulfate 
is  incorporated,  the  heating  being  continued  until  dissolved.  During 
this  treatment  the  pitch  is  hardened  and  its  fusing-point  (Test  i$c: 
cube-in-air  method)  raised  to  about  400°  F.  It  is  thereupon  cut 
back  with  30  to  40  per  cent  anthracene  oil.  The  final  product, 
known  as  "rubber  pitch"  has  a  low  susceptibility,  and  tests  as  fol- 
lows: 

(Test   7)    Specific  gravity  at  77°  F i .  240 

(Test  9^)  Penetration  at  115°  F 55  to  65 

Penetration  at  77°  F 20  to  22 

Penetration  at  32°  F 5  to  9  * 

(Test  ij<r)  Fusing-point  (cube  method) 180  to  190°  F. 

(Test  31)    Free  carbon 33    to  36  per  cent 

Coal  tars  and  coal-tar  pitches  may  be  deodorized  by  treating 
with  formaldehyde  or  paraformaldehyde  in  the  presence  of  acids  or 
alkalies  followed  by  blowing  steam  through  the  heated  mass.82  Coal 


376  COAL  TAR  AND  COAL-TAR  PITCH  XVII 

tars  may  be  hardened  and  toughened,  and  thereby  rendered  less  sus- 
ceptible to  temperature  changes,  by  converting  the  phenols,  cresols, 
etc.,  in  situ,  into  formaldehyde  condensation  products  (i.e.,  phenolic 
resins)  as  follows:  coal  tar  (1000  parts)  is  mixed  with  formal- 
dehyde (10  parts)  and  ammonia  of  sp,  gr.  0.880  (5  parts),  then 
digested  8  hours  at  70°  C.  in  a  closed  vessel,  whereupon  a  catalyst 
(e.g.,  CuSO4  or  FeSCX)  is  added  and  the  mass  blown  with  air  for 
I  o  to  30  hours,  during  which  process  the  temperature  is  gradually 
increased  to  193°  C.  The  resultant  product  has  been  marketed 
under  the  name  "Bitural".88  Similarly,  synthetic  resins  may  be  pro- 
duced from  the  fraction  of  low-temperature  coal  tar,  distilling  be- 
tween 170  and  230°  C.  (containing  phenols),  by  heating  to  100°  C. 
with  aqueous  40  per  cent  formaldehyde  and  a  basic  catalyst,  such  as 
caustic  soda,  pyridine,  trimethylamine,  or  tri-ethylamine,  until  three 
layers  are  formed.  The  upper  layer  consists  of  neutral  oils  and 
unaltered  phenols,  the  middle  layer  is  aqueous,  whereas  the  lower 
layer  consists  of  phenolic  resins.84 

Coal-tar  pitch  may  be  treated  with  chlorine  in  the  presence  of 
a  chlorine  carrier,  which  serves  to  increase  its  lustre,  hardness  and 
fusing-poirit,  resulting  in  a  product  which  resembles  asphalt.85  An 
asphalt-like  product  may  also  be  obtained  by  mixing  coal-tar  pitch 
either  with  the  insoluble  constituents  precipitated  from  coal  tar  by 
treatment  with  benzol,  or  with  cumarone  resin  which  has  been 
heated  to  270°  C .*' 

A  process  of  cracking  at  510-750°  C.  in  a  tube-still  serves  to 
convert  coal  tars  into  a  product  which  sulfonates  completely  upon 
digesting  with  H2SO4.87 

The  percentage  of  free  carbon  in  coal  tars  and  coal-tar  pitches 
may  be  increased  by  heating  under  pressure  between  700  and 
820°  R*8 

The  following  pitches  are  produced  in  small  amounts,  princi- 
pally in  Germany,  as  by-products  in  the  refining  of  coal-tar  deriva- 
tive^: 

Anthracene  Pitch.  (Anthracene-oll-tar  Pitch}.  This  is  ob- 
tained as^a  residue  upon  the  purification  of  anthracene  by  distilla- 
tion^ and  is  characterized  by  being  hard,  black  and  glossy.  Anthra- 
cene pitch  may  be  hardened  by  heating  with  sulfur,  or  with  spent 
irbn  oxide  obtained  in  the  purification  of  coal  gas.90  Anthracene 


XVII  NAPHTHOL  AND  CRESOL  PITCHES  377 

pitch  may  be  used  for  various  purposes,  including  briquette 
binders.91 

Naphthol  Pitch.  This  is  obtained  in  the  refining  of  betanaph- 
thol  or  naphthylamine.92  It  is  a  glossy  black  solid,  fusing  at  about 
120°  C,  and  is  almost  completely  soluble  in  solvent  naphtha  (xylol) 
chloroform  and  pyridine.  Upon  boiling  with  aqueous  caustic  soda 
it  yields  naphthol,  which  may  be  identified  qualitatively.  Its  f  using- 
point  may  be  increased  by  heating  with  formaldehyde  in  the  pres- 
ence of  a  mineral  acid,93  and  a  rubber-like  product  is  obtained  upon 
fluxing  with  a  vegetable  oil  and  adding  fillers.94  Naphthol  pitch 
may  be  used  in  the  manufacture  of  lacquers  and  for  molding  com- 
positions.95 Naphthylamine  pitch  is  obtained  as  a  by-product  in  the 
refining  of  naphthylamine. 

Cresol  Pitch.  This  is  obtained  as  a  residue  in  the  distillation  of 
crude  cresol,  and  is  known  in  Germany  under  the  names  "Karbol- 
pech,"  "Kresolharz"  and  "Phenolpech."  It  has  a  fusing-point  of 
60  to  80°  C.,  a  decided  cresol  odor  on  heating  and  a  brownish-black 
color.  It  is  more  or  less  soluble  in  aqueous  caustic  potash  and  al- 
most completely  soluble  in  alcohol  and  mixtures  of  alcohol  and 
benzol.98  It  is  similarly  used  in  the  manufacture  of  lacquers. 


CHAPTER  XVIII 
WATER-GAS  AND  OIL-GAS  TARS  AND  PITCHES 

Water-gas  tar,  oil-gas  tar  and  their  corresponding  pitches  are 
not  classified  with  "coal  tar"  and  "coal-tar  pitch/'  as  they  are  inter- 
mediate in  their  properties  between  the  latter  and  petroleum 
asphalts,  on  account  of  the  petroleum  products  used  in  their  manu- 
facture. They  are  accordingly  included  in  a  separate  chapter. 

Carburetted  Water-gas  Tar.  The  mechanism  of  this  process 
has  already  been  briefly  described.  A  modern  water-gas  plant  hav- 




Generator    Carbureter ,      Superheater 


Scrubber       Condenser 


FIG.  117, — Lowe  Water-gas  Plant. 

ing  a  capacity  of  1 1/2  to  3  million  cubic  feet  of  gas  per  day  is  illus- 
trated diagrammatically  in  Fig.  117.  This  is  known  as  the  Lowe 
type  of  apparatus.  Either  anthracite  coal  or  coke  may  be  used  as 
fuel.  The  fuel  is  charged  into  the  generator  and  allowed  to  under- 

378 


XVIII  CAREURETTED  WATER-GAS  TAR  379 

go  partial  combustion  by  admitting  a  limited  amount  of  primary  air 
through  the  pipe  A  below  the  bed  of  fuel.  The  gases  then  pass 
downward  through  the  carbureter  and  the  combustion  almost  com- 
pleted by  means  of  a  carefully  regulated  supply  of  secondary  air 
introduced  through  the  valve  B.  From  the  carbureter  the  products 
pass  upward  through  the  superheater,  where  the  temperature  may 
be  controlled  by  admitting  a  tertiary  supply  of  air  through  the  valve 
C)  and  the  products  of  combustion  finally  passed  into  the  atmos- 
phere through  the  stack  D. 

When  the  fuel  in  the  gas-generator  has  been  properly  ignited, 
and  the  carbureter  and  superheater  brought  to  the  required  tem- 
peratures, the  air  blasts  are  cut  off  in  the  sequence :  C,  B,  and  A9  and 
the  stack  valve  D  closed.  Steam  is  introduced  into  the  generator 
through  the  valve  E  below  the  bed  of  incandescent  fuel  and  results 
in  the  production  of  "blue-gas,"  according  to  the  following  reaction: 
C  +  H2O  =  CO  +  H2.  This  is  passed  into  the  carbureter  where 
it  mingles  with  a  spray  of  carbureting  oil  consisting  of  "gas  oil"  or 
"fuel  oil"  introduced  through  F.  The  mixture  is  passed  downward 
through  the  carbureter  whereby  the  oil  becomes  vaporized.  Frorri 
the  carbureter,  the  gases  are  passed  up  through  the  superheater,  the 
temperature  of  which  is  very  carefully  regulated  at  1200-1300°  F. 
to  crack  the  oil  vapors  into  permanent  gases,  and  this  incidentally 
results  in  the  formation  of  tarry  matters. 

The  formation  of  carbon  monoxide  and  hydrogen  by  the  action 
of  steam  on  incandescent  fuel  results  in  a  lowering  of  the  tempera- 
ture, on  account  of  the  absorption  or  storing  up  of  thermal  energy, 
so  that  it  becomes  necessary  to  turn  off  the  steam  and  reintroduce 
the  air.  The  "blowing  up"  process  is  then  repeated.  At  the  same 
time  the  oil  spray  is  turned  off  the  carbureter,  as  its  temperature  has 
fallen  to  a  point  below  which  the  oil  would  not  be  superheated  suffi- 
ciently to  convert  it  into  a  permanent  gas.  The  "blowing"  or  "up 
run"  lasts  three  to  five  minutes,  and  the  "gas  making"  or  "down 
run"  lasts  two  to  four  minutes. 

The  water-gas  and  accompanying  tarry  vapors  derived  from 
the  gas  oil  are  passed  from  the  superheater  through  the  pipe  G  into 
a  wash-box  which  corresponds  to  the  hydraulic  main  in  a  coal-gas 
plant  The  vaporization  of  water  in  the  wash-box  reduces  the 
temperature  of  the  gases  from  1200  to  190°  F.  The  gases  next 


380  WATER-GAS  AND  OIL-GAS  TARS  AND  PITCHES  XVIII 

pass  upward  through  a  scrubber  and  are  then  passed  downward 
through  a  water-cooled  condenser  which  reduces  their  temperature 
to  140-150°  F.,  and  thence  into  a  relief  gas-holder.  Most  of  the 
tar  is  condensed  in  the  wash-box  and  smaller  quantities  in  the  scrub- 
ber and  condenser.  An  exhauster  draws  the  gases  through  the  fore- 
going train  of  apparatus  and  then  forces  them  through  a  tar  extrac- 
tor, to  remove  the  last  traces  of  tar*  The  temperature  of  the  gases 
as  they  pass  through  the  tar  extractor  is  in  the  neighborhood  of 
110-115°  F.  They  are  finally  passed  through  the  purifier  filled 
with  trays  of  ferric  oxide  to  remove  the  sulfur  compounds,  and 
thence  into  the  main  gas  holder. 

The  carbureting  oil,  known  also  as  "gas  oil"  or  "enriching  oil" 
varies  in  composition,  depending  upon  the  character  of  the  petro- 
leum from  which  it  is  derived.  Experience  demonstrates  that  oils  ob- 
tained from  a  paraffin-base  petroleum  generate  the  greatest  propor- 
tion of  gas  and  the  smallest  quantity  of  tar.  Oils  containing  unsatu- 
rated  straight-chain  hydrocarbons  are  less  efficient,  and  those  con- 
taining unsaturated  ring  hydrocarbons  are  almost  valueless.  The 
yield  of  tar  expressed  in  percentage  by  volume,  based  on  the  various 
types  of  petroleum  used,  is  as  follows: 

Paraffin-base  naphtha 2-  4  per  cent 

Paraffin-base  gas  oil 6-10  per  cent 

Paraffin-base  crude  oil 8-12  per  cent 

Asphaltic-base  gas  oil 10-15  Per  cent 

Asphaltic-base  crude  oil 12-18  per  cent 

The  quantity  of  carbureting  oil  ordinarily  used  varies  from  2.5 
to  4.5  gal.  per  1000  cu.  ft.  of  gas  manufactured,  depending  upon  the 
statutory  requirements  in  the  territory  where  the  gas  is  distributed, 
as  to  its  illuminating  and  heating  values. 

Properties  of  Water-Gas  Tar.  On  account  of  the  low  specific 
gravity  of  water-gas  tar,  it  readily  forms  an  emulsion  with  the  as- 
sociated water  and  separates  with  great  difficulty.  The  water  thus 
retained  may  run  as  high  as  85  per  cent  and  the  greater  the  per- 
centage of  water  present,  the  more  viscous  will  be  the  emulsion.1 
The  water  is  practically  free  from  ammonia  compounds,  thus  differ- 
ing from  coal  tar,  and  the  tar  is  very  much  thinner  in  consistency, 
containing  but  a  small  amount  of  free  carbon.  The  methods  for 
dehydrating  crude  water-gas  tar  are  similar  to  those  used  for  coal 


XVIII  ,          PROPERTIES  OF  WATER-GAS  TAR  381 

tars.    The  dehydrated  water-gas  tar  complies  with  the  following 
tests : 

(Test    i)    Color  in  mass Black 

(Test   la)  Homogeneity  to  the  eye Uniform 

(Test    2^)  Homogeneity  under  microscope Absence  of  carbonaceous 

matter 

(Test   7)    Specific  gravity  at  77°  F x.oo~i.x8 

(Test    8)    Viscosity  at  212°  F.  (100  cc.) 25-50 

(Test  i5<r)  Fusmg-point  (cube  method) Less  than  o°  to  10°  F. 

(Test  1 6)    Volatile  matter  at  50x3°  F.,  5  hrs 60-85  per  cent 

(Test  1 6£)  Distillation: 

By  weight 

Up  to  1 10°  C.  (Naphtha) o    -  5     per  cent  (Sp.  gr.  o.  85-0. 90) 

iio-i7o°C    (Light  oils) 0.5-  5.0  per  cent  (Sp.  gr.  0.88-0.90) 

170-235°  C.    (Middle  oils) 5    ~35     per  cent  (Sp.  gr.  o. 98-1 .00) 

235-270°  C.    (Heavy  oils) 7-30     per  cent  (Sp.  gr.  i  .00-1 .07) 

270-350°  C.    (Anthracene  oil) . .    10    -25      per  cent  (Sp,  gr.  1 . 07-1 .  10) 
Residue          (Water-gas-tar 

pitch) «...   20    -70     per  cent 

(Test  17*)  Flash-point Low 

(Test  19)    Fixed  carbon 10-20  per  cent 

(Test  21)     Solubility  in  carbon  disulfide 95    -100  per  cent 

Non-mineral  matter  insoluble 0.2-    5  per  cent 

Mineral  matter o    -    \  per  cent 

(Test  22)    Carbenes o    -    2  per  cent 

(Test  23)    Solubility  in  88°  petroleum  naphtha 20    -  75  per  cent 

(Test  26)    Carbon 90    -  95  P^r  cent 

(Test  27)    Hydrogen 3    -    6  per  cent 

(Test  28)     Sulfur o.  5-2.0  per  cent 

(Test  29)    Nitrogen o.  5-1  .o  per  cent 

(Test  30)    Oxygen i    -    2  per  cent 

(Test  32)    Naphthalene Less  than  10  per  cent 

(Test  33)     Solid  paraffins o    -    5  per  cent 

(Test  34^)  Sulfonation  residue i    -  25  per  cent 

(Test  37*)  Saponifiable  constituents Tr.  -    2  per  cent 

(Test  39)     Diazo  reaction Yes 

(Test  40)    Anthraquinone  reaction Yes 

Water-gas  tars  consist  principally  of  aromatic  hydrocarbons  and 
contain  less  naphthalene  than  coke-oven  tars,  negligible  phenols  and 
bases,  also  small  amounts  of  solid  paraffins  and  considerable  naph- 
thalenes. According  to  Downs  and  Dean,2  water-gas  tar  contains 
substantial  amounts  of  benzene,  toluene,  xyienes,  naphthalene  and 
anthracene.  The  nitrogenous  bases  and  phenols  are  absent  or 
nearly  so.  Weiss  reports  further  that  the  percentage  of  free  carbon 
varies  from  1.04  to  1.087  per  cent,  with  water-gas  tars  ranging  in 
specific  gravity  from  i. 078-1. 090.*  Water-gas  tar  may  be  vulcan- 
ized by  heating  with  5  to  8  per  cent  of  sulfur.4 


382 


WATER-GAS  AND  OIL-GAS  TARS  AND  PITCHES 


XVII] 


Oil-gas  Tars.  These  are  manufactured  from  petroleum  alon< 
without  the  use  of  coal  or  coke.  Several  methods  have  been  used 
all  embodying  the  same  principle  but  differing  in  detail,  the  mosl 
important  of  which  are  as  follows: 

Pintsch  Gas.  This  is  manufactured  by  spraying  gas-oil  derived 
from  petroleum  in  a  closed  retort  constructed  of  iron  or  fire  clay  and 
heated  to  a  temperature  of  900  to  1000°  C.  by  combustion  of  oil, 
gas  or  tar  underneath.  The  shape  of  the  retort  is  shown  in  Fig. 
1 1 8.  The  vapors  pass  to  the  rear  and  thence  downward  and  through 
a  lower  chamber  into  the  hydraulic  main  in  front  The  gases  are 
passed  successively  through  a  scrubber,  condenser  and  purifier. 


O/J  and  Sfectm 


Oilond 
Steam 


FIG.  1 1 8.— Pintsch  Gas  Retort 


fffiffi^"$^^ 
FIG.  119.— -Oil-water  Gas  Plant. 


Pintsch  gas  is  used  extensively  for  railroad  and  buoy  lighting.  It 
may  be  stored  in  holders  under  a  pressure  of  5  to  25  atmospheres, 
without  suffering  in  illuminating  power,  as  would  prove  to  be  the 
case  with  most  other  gases  adapted  for  lighting  purposes. 

About  10  per  cent  tar  is  recovered  in  the  rintsch  process,  the 
characteristics  of  which  will  be  described  under  the  heading  "oil-gas 
tar"  below. 

Oil-water  Gas.  This  process  is  used  almost  exclusively  on  the 
Pacific  coast  for  manufacturing  illuminating  gas,  owing  to  the  ab- 
sence of  coal  deposits.  The  installation  is  shown  diagrammatically 
in  Fig.  119,  and  operates  similar  to  a  water-gas  plant,  except  that 
petroleum  is  used  instead  of  coal  or  coke. 

It  requires  about  8  to  8j^  gal  of  fuel  oil  per  1000  cu.  ft  of  gas 


XVIII  REFINING  OF  WATER-GAS  AND  OIL-GAS  TARS  383 

(550—625  B.t.u.)  of  which  about  one-fifth  is  required  for  heating 
and  four-fifths  for  gas-making.  Higher  temperatures  are  used  for 
cracking  than  is  the  case  in  the  manufacture  of  Pintsch  gas  or  Blau 
gas,  in  consequence  of  which  heavier  tars  are  obtained,  higher  in 
free  carbon  and  aromatics. 

Oil-water-gas  tar  has  also  been  termed  "fuel-oil  gas  tar"  and 
"reformed-gas  tar."  5  At  room  temperatures  it  has  a  soft,  semi- 
solid  to  almost  solid  consistency.  Those  produced  at  medium  tem- 
peratures have  a  specific  gravity  at  60°  F.  of  1.15  to  1.20;  insoluble 
in  benzol  12  to  15  per  cent;  sulfonation  residue  2  to  5  per  cent. 
Those  produced  at  high  temperatures  have  a  specific  gravity  at 
60°  F.  of  1.30  to  1.35;  insoluble  in  benzol  25  to  40  per  cent;  sul- 
fonation residue  less  than  0.5  per  cent. 

Blau  Gas.  This  is  a  further  development  of  Pintsch  gas,  and  is 
made  by  cracking  oil  vapors  at  a  temperature  lower  than  in  the 
Pintsch  process  (i.e.,  550  to  600°  C.),  but  in  a  similar  form  of  re- 
tort. The  resulting  gases  are  first  purified  by  passing  in  the  usual 
manner  through  hydraulic  mains,  coolers,  cleaners  and  scrubbers  to 
remove  the  tar,  which  amounts  to  4-6  per  cent  of  the  oil  used,  and 
then  compressed  in  a  three-  or  four-stage  compressor  to  100  atmos- 
pheres, which  causes  the  high  boiling-point  constituents  to  liquefy 
and  absorb  a  large  proportion  of  the  non-liquefiable  gases.  The 
excess  of  the  latter  is  used  for  running  the  compressor  and  heating 
the  retorts. 

The  compressed  Blau  gas  is  so  constituted  that  upon  releasing 
the  pressure,  the  dissolved  and  liquefied  constituents  are  evolved  in 
such  proportions  that  the  composition  of  the  gaseous  mixture  re- 
mains constant.  Blau  gas  is  used  principally  for  marine  lighting 
purposes  and  is  transported  in  cylinders  of  about  I  cu.  ft  capacity, 
carrying  20  Ib.  of  the  compressed  gas,  which  will  expand  to  about 
250  cu.  ft  at  atmospheric  pressure.  Its  illuminating  value  is 
greater  than  that  of  Pintsch  gas. 

The  tar  recovered  from  the  Blau  gas  process  (about  15—20 
per  cent),  is  similar  in  its  physical  and  chemical  properties  to  the 
oil-gas  tars  described  previously.6 

Properties  of  Oil-gas  Tars.  Dehydrated  oil-gas  tars  produced 
by  the  Pintsch  process,  the  Blau  gas  process,  and  the  oil-water  gas 
process  comply  with  the  characteristics  given  on  the  following  page* 

Oil-gas  tar  may  be  vulcanized  by  heating  with  sulfur,7  or  by 
treating  with  sulfur  dichloride.8 

Refining  of  Water-gas  and  Oil-gas  Tars.  Oil-gas  and  water- 
gas  tars  when  suitably  dehydrated  may  be  distilled  in  accordance 
with  the  methods  used  for  "coal  tar."  Sometimes,  either  water-gas- 


384 


WATER-GAS  AND  OIL-GAS  TARS  AND  PITCHES 


XVIII 


Oil-gas  Tars 

Low  Temperature 
(Pintsch-  and  Blau- 
gas  Tars) 

I 
High  Temperature 
(Oil-water-gas  Tars) 

(Test   i)    Color  in  mass.  *  

Black 

Uniform 
Comparatively  free 
from  carbonaceous 
matter. 
0,95-1,10 
25-50 
o 

Black 
Gritty 
Contains   consider- 
able   carbonaceous 
matter. 

i.iS-i-35 
Over  50 
o  to  5 

30-100°  F. 

(Test  id)  Homogeneity  to  the  eye  

(Test   2^)  Homogeneity  under  microscope.  

(Test   7)    Specific  gravity  at  77°  F  

(Test    8*)  Viscosity  at  212°  F.  (100  ml.)  

(Test   9*:)  Consistency  at  77°  F  

(Test  15^)  Fusing-point  (R.  &  B,  method)  

(Test  15^)  Fusing-point  (Cube  method)  .  .  .*  

<0-20°F. 

35-70  per  cent 
30-75  per  cent 

(Test  1  6)    Volatile  at  500°  F.  in  5  hrs.  .  .  

25-50  per  cent 

20-50  per  cent 
1.05-1.12 
50-80  per  cent 
ioo-i5o°C. 
Low 
15-35  percent 
70-90  per  cent 
10-30  per  cent 
0-0.5  per  cent 
0-2  per  cent 
25-70  per  cent 
<  i  per  cent 
1-2  per  cent 
0-5  per  cent 
Trace 
Trace  to  10  per  cent 
Trace 
Yes  (marked) 
Yes 

(Test  1  6b)  Distillation  Test: 
Distillate  to  315°  C.  (vol.)  

Sp.  gr.  ditto  at  6o°/6o°  C  

Residue  at  31  5°  C.  (wt.)  

25-70  per  cent 

Fusing-point  ditto  (R.  &  B.  method)  . 
(Test  170)  Flash-point      .   ,  

Low 

10-25  per  cent 
99-100  per  cent 
0-0.2  per  cent 
0-0.5  per  cent 
0-2  per  cent 
50-85  per  cent 
<  i  per  cent 
1-2  per  cent 
Trace 
0-5  per  cent 
20-40  per  cent 
Trace 
Yes  (slight) 
Yes 

(Test  19)    Fixed  carbon  

(Test  2i)    Soluble  in  carbon  disulfide  

Non-mineral  matter  insoluble  ........ 

Mineral  matter  

(Test  22)    Carbenes  

(Test  23)    Soluble  in  88°  petroleum  naphtha  
(Test  28)    Sulfur  

(Test  30)    Oxygen  .    .  .  *  

(Test  32)    Naphthalene  

(Test  33)    Solid  paraffins   

(Test  34^)  Sulfonation  residue  

(Test  37*)  Saponifiable  constituents  

(Test  39)    Diazo  reaction     

(Test  40)    Anthraouinone  reaction  

tar  pitch  or  oil-gas-tar  pitch  is  mixed  with  coal-tar  pitch  in  suitable 
proportions. 

Properties  of  Water-gas-tar  Pitch  and  Qil-gas-tar  Pitch.  Water- 
gar-tar  and  oil-gas-tar  pitches  may  be  distinguished  from  coal-tar 
pitches  by: 

(1)  The  small  percentage  of  "free  carbon"  (non-mineral  mat- 
ter insoluble  in  carbon  disulfide). 

(2)  The  possible  presence  of  paraffin  wax  (when  non-asphaltic 
or  semi-a&phaltic  petroleums  are  used). 

On  the  other  hand,  water-gas-tar  pitch  may  be  distinguished 
from  oil-gas-tar  pitch  by  the  following: 


XVIII          WATER-GAS-TAR  PITCH  AND  OIL-GAS-TAR  PITCH 


385 


1 I )  Lower  specific  gravity  of  water-gas-tar  pitch. 

(2)  Larger  percentage  of  sulfonation  residue  from  oil-gas-tar 
pitch.     The  sulfonated  constituents  are  soluble  in  water,  which 
serves  to  differentiate  them  from  lignite-  and  shale-tars  and  pitches. 

Water-gas-tar  and  oil-gas-tar  pitches  comply  with  the  following 
tests : 


Water-gas-tar 
Pitch 

Oil-gas-tar 
Pitch 

(Test    |}    Color  in  mass    .       

Black 
Uniform 
Small  amount  o 
Variable 
Conchoidal 
Bright 
Black 
1.10-1.25 

O-IOO 
>IQO 

Variable 
Variable 
80-275°  F. 
100-300°  F. 
110-320°  F. 

5-i5 
300-400°  F. 

25-45 
75-98 
2-25 
o-* 

5-10 

50-70 

<4 
0-2 

0-5 
0-15 

O-I 

Yes  (*) 
Yes 

Black 
Uniform 
f  carbon  visible 
Variable 
Conchoidal 
Bright 
Black 
I.I5-I-35 

O-IOO 
>IOO 

Variable 
Variable 
80-275°  F. 
100-300°  F. 
i  10-320°  F, 
5-15 
300-400°  F. 
20-35 
70-98 
2-30 
o~i 
5-10 

60-80 
<4 

O-2 

0-5 
20-40 

O-I 

Yes  (*) 
Yes 

(Test   20)  Homogeneity  to  the  eye  

(Test   2^)  Homogeneity  under  the  microscope  

(Test   4)    Fracture  

(Test    5)    Lustre  

(Test   6)    Streak            

nV«t    V\    Snecific  crravitv  at  *77°  F    

(Test   9^)  Penetration  at  77°  F  i  .  . 

(Test   (\£\  Susceptibility  index       

(Test  10)    Ductility  

(Test  n)    Tensile  strength  at  77°  F  

(Test  1  50)  Fusing-point  (K.  and  S.  method)  

(Test  i$b)  Fusing-point  (R.  and  B.  method)  

(Test  i  5^)  Fusing-point  (cube  method)  

(Test  1  6)    Volatile  matter  500°  F.,  5  hrs.  (per  cent)  .  . 
(Test  170)  Flash-point                 

(Test  19)    Fixed  carbon  (per  cent)     

(Test  21)    Solubility  in  carbon  disulfide  (per  cent)  
Non-mineral  matter  insoluble  (per  cent)  — 
Mineral  matter  (per  cent)  ...,.,,,,,, 

(Test  22)    Carbencs  (per  cont)        »  .  «  

(Test  23)    Solubility  in  88°  petroleum  naphtha  (per 
cent)  

(Test  28)    Sulfur  (per  cent)  «  

rry«jt  -30^    Oxvcren  (oer  cent}  

(Test  33)    Solid  paraffins  (per  cent)  

(Test  34^)  Sulfonation  residue  (per  cent)  ............ 

(Test  37^)  Saponifiable  matter  (per  cent)  

(Test  **(\\    Diazo  reaction     .........   ,    »  »  ,  

(Test  40)    Anthratjuinone  reaction  ............  r  ,  n  r  - 

Slight— contain  but  a  trace  of  phenols. 


Both  of  these  pitches  are  largely  susceptible  to  changes  in  tem- 
perature, they  are  highly  resistant  to  the  prolonged  action  of  mois- 
ture, and  they  are  adapted  for  manufacturing  low-priced  solvent 
paints  because  of  their  ready  solubility  in  "coal-tar  naphtha/' 


CHAPTER  XIX 
FATTY-ACID  PITCH,  BONE  TAR  AND   BONE-TAR  PITCH 

These  are  classified  together  because  all  are  derived  from  sub- 
stances containing  animal  or  vegetable  fats  or  oils,  although  in 
manufacturing  bone  tar  and  bone-tar  pitch  the  crude  materials  carry 
but  a  small  proportion. 

FATTY-ACID  PITCH 

Various  generic  terms  have  been  used  to  designate  this  prod- 
uct, including  candle  tar,  "Kerzenteer"  (German)  "goudron" 
(French),  candle  pitch,  fat  pitch  and  "Fettpech"  (German).  Spe- 
cific names  have  also  been  applied,  descriptive  of  the  raw  materials 
used  in  producing  the  pitch,  such  as  stearin  pitch,  palm-oil  pitch, 
bone-fat  pitch,  cotton-seed-oil  pitch,  cotton  pitch,  cotton-stearin 
pitch,  cotton-seed-foots  pitch,  corn-oil  pitch,  corn-oil-foots  pitch, 
packing-house  pitch,  garbage  pitch,  sewage  pitch,  fullerVgrease 
pitch,  wool  pitch,  wool-grease  pitch,  wool-fat  pitch,  cholesterol 
pitch,  cotton-oil  pitch,  cotton-seed-oil-foots  pitch  and  stearin-wool 
pitch. 

The  fatty-acid  pitches  are  obtained  as  by-products  in  the  follow- 
ing manufacturing  processes  : 

(  i  )  Production  of  candle  and  soap  stocks. 

(2)  Refining  vegetable  oils  by  means  of  alkalies. 

(3)  Refining  refuse  greases. 

(4)  Treatment  of  wool  grease. 

The  raw  materials  used  include  the  vegetable  oils  and  fats,  ani- 
mal oils,  fats  and  waxes  (wool  grease),  also  the  waste  greases  de- 
rived from  the  foregoing.  Vegetable  and  animal  fats  and  oils  are 
combinations  of  the  fatty  acids  with  glycerin,  known  as  "triglycer- 
ides,"  and  illustrated  by  the  following  generic  formula,  in  which  "R" 
represents  any  fatty  acid  radicle: 


C3H5eOR 
NOR 


XIX  FATTY-ACID  PITCH  387 

Fats  and  oils  may  be  purified  or  refined  in  two  ways  : 

(1)  By  treating  vegetable  oils  with  a  small  amount  of  caustic 
soda  to  remove  the  coloring  matter,  free  fatty  acids  and  other  im- 
purities, without,  however,  breaking  up  the  triglycerides.     This 
process  is  used  for  refining  vegetable  oils  when  they  are  to  be  used 
for  edible  purposes.    The  residue  is  treated  with  mineral  acid  to 
break  up  the  soaps,  and  then  distilled  with  steam  to  recover  the 
fatty  acids,  whereupon  a  residue  of  fatty-acid  pitch  is  obtained. 

(2)  By  decomposing  or  "hydrolyzing"  the  triglycerides  into 
glycerin  and  free)  fatty  acids,  and  then  distilling  the  latter  with 
steam,  whereby  fatty-acid  pitch  is  obtained  as  a  residue.    The  object 
of  distilling  the  fatty  acids  is  to  improve  their  color  or  odor  and 
thereby  adapt  same  (a}  for  the  manufacture  of  candles  (which  are 
commonly  light-colored  or  white),  or  (b]  for  manufacturing  soaps 
(such  as  toilet  soaps,  etc.)  which  must  be  odorless  and  preferably 
light-colored. 

Production  of  Candle  and  Soap  Stocks.  These  are  obtained 
from  various  animal  and  vegetable  oils  and  fats,  also  from  waste 
greases.  It  is  always  necessary  to  subject  the  fatty  acids  to  a  proc- 
ess of  hydrolysis  and  steam  distillation  for  producing  candles,  but 
not  for  manufacturing  soaps,  unless  the  fatty  acids  are  too  dark  in 
color  for  the  character  of  soap  required  or  possess  a  disagreeable 
odor,  in  which  event  they  are  purified  by  distillation.  Various 
methods  of  hydrolysis  may  be  used,  but  they  all  depend  upon  the 
same  reaction,  in  which  the  triglyceride  combines  with  water  and 
decomposes  into  glycerin  and  fatty  acids,  as  illustrated  in  the  fol- 
lowing equation: 

OR  OH 

-OH 


C3H5A)R  +  3H-OH  -  CaHsf-OH  +  jR-OH 
fc>OR  XOH 

Triglyceride  Water  Glycerin  Free  Fatty  Acid 

(fat  or  oil) 

It  is  necessary  to  hydrolyze  the  fats  or  oils  before  distilling  the 
fatty  acids,  since  the  triglycerides  themselves  are  not  capable  of  be- 
ing distilled  without  decomposition.  The  following  methods  of 
hydrolysis  have  been  used: 

(a)  Hydrolysis  by  Means  of  Water.  Formerly,  water  alone 
was  used  for  the  purpose,  the  fat  or  oil  being  heated  in  an  autoclave 
with  30  per  cent  of  its  weight  of  water  at  220  Ib.  pressure  (corre- 
sponding to  a  temperature  of  200°  C.)  for  eight  to  twelve  hours. 


388         FATTY-ACW  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

This  decomposes  the  triglyceride  into  fatty  acids  and  glycerin,  but 
with  water  alone  it  is  difficult  to  break  down  the  fat  completely. 
It  has  been  found  that  the  addition  of  3  per  cent  of  lime  or  mag- 
nesium oxide,  and  preferably  the  latter,  assists  the  reaction  and 
produces  a  larger  yield  of  a  better  product,  and  at  a  much  lower 
temperature.  Accordingly,  the  fat  or  oil  is  heated  at  120  Ib.  pres- 
sure in  a  horizontal  or  vertical  cylindrical  vessel  provided  with 
a  stirring  device,  with  20  to  25  per  cent  by  weight  of  water  and 
3  per  cent  of  lime  or  magnesium  oxide.  The  breaking  down  of 
the  fat  is  practically  complete  at  the  end  of  eight  to  ten  hours,  and 
in  addition  the  color  is  very  much  better,  as  there  is  less  decom- 
position, due  to  the  lower  temperature  employed.  The  fats  or  oils 
used  for  this  purpose  may  consist  of  animal  or  vegetable  tallow, 
palm  oil,  bone  fat,  lard-  or  cotton-seed  stearin  (crystallized  at  low 
temperatures  from  lard  or  cotton-seed  oil  respectively),  shea  butter, 
etc. 

At  the  end  of  the  process,  the  free  fatty  acids  rise  to  the  sur- 
face and  are  skimmed  off,  leaving  the  aqueous  liquor  containing  the 
glycerin  (together  with  the  hydrated  lime  or  magnesia,  when  the 
Fatter  are  used).  The  glycerin  is  recovered  by  a  special  process 
which,  however,  does  not  fall  within  the  scope  or  this  treatise.  The 
fatty  acids  are  subjected  to  steam  distillation  to  deodorize  and 
whiten  them,  also  to  purify  them  by  separating  any  non-hydrolyzed 
fat  The  fatty  acids  are  run  into  lead-lined  tanks  wrhere  they  are 
first  treated  with  dilute  sulfuric  acid  to  remove  any  traces  of  mag- 
nesium oxide,  etc.,  then  washed  with  water,  heated  to  expel  the 
moisture,  after  which  they  are  fed  into  a  retort  and  distilled  with 
superheated  steam  with  or  without  the  use  of  vacuum.  The  fatty 
acids  suitable  for  distillation  should  not  contain  more  than  5  per 
cent  of  non-hydrolyzed  fat  (neutral  fat)  nor  more  than  0.2  per  cent 
of  mineral  matter.  To  obtain  a  distillate  of  good  quality,  care 
should  be  taken  not  to  distil  the  fatty  acids  at  too  high  a  tempera- 
ture, as  they  are  extremely  susceptible  to  overheating  and  decom- 
position into  dark-colored  hydrocarbons  (unsaponifiable),  which 
would,  of  course,  depreciate  the  value  of  the  product.1  The  still 
should  be  constructed  so  that  the  flames  will  not  come  into  direct 
contact  with  the  bottom  and  cause  local  overheating.  The  tem- 
perature of  the  material  in  the  still  should  preferably  be  maintained 
between  230  and  250°  C,  and  although  in  certain  instances  it  is 
permissible  to  reach  a  temperature  of  270°  C.,  under  no  circum- 
stances should  this  be  exceeded. 

Two  methods  are  used  for  conducting  the  distillation.  The 
first  consists  in  continuously  replacing  the  tatty  acids  as  they  distil, 
with  an  equivalent  quantity  of  undistilled  material,  as  long  as  the 
distillate  snows  a  satisfactory  color  and  is  free  from  unsaponifiable 


XIX 


FATTY-ACW  PITCH 


389 


hydrocarbons.  The  effect  of  the  distillation  is  to  concentrate  the 
impurities  and  unsaponified  (neutral)  fats  or  oils  in  the  still.  A 
typical  installation  is  illustrated  in  Fig.  I20.2 

The  heating  element  in  the  still,  a,  consists  of  two  copper  coils 
of  approximately  270  square  feet  (25  square  meters)  mean  sur- 
face. Steam  at  about  450  pounds  per  square  inch  (32  kg.  per 
sq.  cm. )  gage  pressure  is  supplied  by  a  motor-driven  compressor,  b. 
Vacuum  is  maintained  at  7  to  10  mm,  of  mercury  by  use  of  steam 
ejectors,  c.  Approximately  10,000  pounds  (4536  kg.)  of  crude 
fatty  acid  are  charged  to  the  still  at  the  start  of  a  run,  and  there- 


To  Primary 

Evacuating 

System 


FIG.  120. — Distillation  of  Fatty  Acids. 

after  for  about  20  hours  the  feed  is  continuous  to  maintain  an  even 
level.  The  crude  stock  going  to  the  still  is  preheated  by  passing 
through  a  heat  exchanger,  d,  which  also  serves  as  a  partial  con- 
denser for  the  fatty  acid  vapors.  Most  of  the  distillate  is  con- 
densed in  the  jacketed  coolers,  e.  A  small  amount  of  stock  is  con- 
densed and  baffled  out  in  separator  /  and  measured  in  receiver  g. 
The  bulk  of  the  distillate  is  received  in  h  and  pumped  out,  under 
vacuum,  to  storage.  The  residue  in  the  still  a  consists  of  soft  fatty- 
aqid  pitch. 

The  second  method  consists  in  replacing  the  distilled  fatty  acids 
for  but  sixteen  to  twenty-four  hours,  then  discontinuing  the  addi- 


390         FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

tion,  and  distilling  the  contents  of  the  retort  until  the  distillate 
ceases  to  be  of  suitable  quality,  as  is  evidenced  by  a  change  in  its 
color.  The  residue  consisting  of  soft  fatty-acid  pitch  is  then  drawn 
off  into  a  separate  still  known  as  the  4<pitch  still,"  the  first  still 
recharged,  and  the  process  repeated,  until  after  a  sufficient  number 
of  distillations,  a  sufficient  quantity  of  soft  fatty-acid  pitch  accu- 
mulates for  further  treatment.  It  is  claimed  that  the  second 
method  gives  better  results  and  yields  a  distillate  lighter  in  color, 
containing  a  smaller  percentage  of  hydrocarbons. 

In  either  case  the  soft  residue  is  distilled  separately  with  super- 
heated steam  and  vacuum.  When  the  neutral  fats  increase  in  con- 
centration to  12  to  15  per  cent  they  commence  to  decompose  into 
hydrocarbons,  some  of  which  distil  with  the  fatty  acids  and  some  re- 
maining with  the  residue.  On  distillation,  the  saturated  fatty-acids 
pass  over  first  and  the  residue  contains  an  increasing  proportion  of 
unsaturated  and  hydroxy-acids,  such  as  hydroxy-stearic  acid,  which 
at  higher  temperatures  is  converted  into  iso-oleic  acid.  At  still 
higher  temperatures  the  fatty  acids  are  converted  into  hydro-car- 
bons, which  are  principally  unsaturated.  The  final  residue  consti- 
tutes the  so-called  "fatty-acid  pitch"  which  amounts  to  between  2.5 
and  5  per  cent  of  the  fatty-acids  distilled. 

(b)  Hydrolysis  by  Means  of  Concentrated  Sulfuric  Acid?  The 
fats  or  oils  are  first  freed  from  moisture  by  heating  to  a  tempera- 
ture of  120°  C.  It  is  essential  that  all  the  moisture  be  removed  to 
prevent  excessive  decomposition.  The  mass  is  then  rapidly  mixed 
with  4  to  6  per  cent  of  concentrated  sulfuric  acid  (66  to  67°  Be.) 
and  heated  in  a  cylindrical  vessel  provided  with  a  mechanical  agi- 
tator. The  heating  is  continued  just  long  enough  to  break  up  the 
triglycerides  and  no  longer.  The  sulfonated  mass  is  then  imme- 
diately run  into  boiling  water  and  agitated  by  a  steam  jet  until  the 
sulfonated  acids  hydrolyze.  The  mass  is  then  allowed  to  stand 
quietly  until  the  free  fatty  acids  rise  to  the  surface,  leaving  the 
glycerol  and  sulfuric  acid  in  the  lower  layer. 

The  fatty  acids  produced  in  this  manner  are  dark  colored  and 
must  be  distilled.  They  are  first  washed  with  water  until  neutral, 
then  heated  to  expel  the  moisture  and  finally  distilled  with  super- 
heated steam,  with  or  without  a  vacuum  as  previously  described, 
whereupon  a  residue  of  soft  fatty-acid  pitch  is  obtained.  According 
to  modern  practice,  this  residue  is  again  treated  with  concentrated 
sulfuric  acid  to  hydrolyze  any  neutral  fats  remaining,  and  inci- 
dentally remove  the  accumulated  mineral  matter  (including  any 
copper  or  iron  derived  from  the  stills).  It  is  then  washed  free  from 
the  acid  and  redistilled,  leaving  a  residue  of  medium  to  hard  fatty- 
add  pitch.  The  dark-colored  distillate,  known  as  "still  returns," 


XVIII  FATTY-ACID  PITCH  391 

is  worked  up  in  small  quantities  with  the  crude  fatty  acids  under 
going  their  first  distillation. 

The  yield  of  stearin  known  in  this  case  as  "distillation  stearin" 
is  greater  than  that  obtained  in  the  aqueous  process  of  hydrolysis, 
due  to  the  fact  that  some  of  the  olein  (in  this  case  known  as  "dis- 
tillation  olein"  or  "distilled  olein")  is  converted  into  a  solid  prod- 
uct (consisting  of  stearolactone,  isomeric  oleic  acid,  etc.).  The 
olein  and  stearin  are  separated  by  cooling,  exactly  as  in  the  fore- 
going process,  A  smaller  yield  of  glycerin  is  obtained  due  to  its 
partial  decomposition  by  the  acid,  and  that  of  fatty-acid  pitch  is 
also  less  and  of  a  darker  color. 

To  avoid  losing  the  glycerin,  which  constitutes  one  of  the  most 
important  and  highest  priced  products,  a  "mixed  process"  is  now 
used  consisting  of  a  combination  of  the  foregoing.  ^ 

(c)  Hydrolysis  by  the  "Mixed  Process"     This  is  a  combina- 
tion of  the  two  foregoing  processes,  and  consists  in  first  hydrolyz- 
ing  the  fats  or  oils  in  an  autoclave  with  water  and  an  alkaline  accel- 
erating agent  (such  as  lime  or  magnesium  oxide),  and  in  this  way 
recovering  the  full  amount  of  glycerin.    The  resulting  fatty ^  acids 
are  dehydrated  and  treated  with  concentrated  sulfuric  acid  in  ac- 
cordance with  process  (b)  to  increase  the  yield  of  stearin  and  com- 
plete the  hydrolysis  of  any  neutral  fat  which  may  have  escaped  the 
first  treatment,  and  thus  minimize  the  formation  of  hydrocarbons 
in  the  distillate, 

(d)  Hydrolysis  by  Means  of  Sulfo-compounds.    This  process, 
known  as  the  E.  Twitchell  method,  is  rapidly  replacing  the  others, 
and  is  now  employed  in  soap  factories  for  treating  the  fats  or  oils 
before  soap-making,  as  it  separates  a  purer  glycerin  and  at  the  same 
time  results  in  a  greater  yield  (88  to  90  per  cent  of  the  theoretical 
quantity  contained  in  the  fat  or  oil  w.  80  to  84.  per  cent  obtained 
in  the  direct  caustic  soda  saponification  method  for  soaps).    More- 
over, the  liquor  separated  in  the  Twitchell  process  is  not  contami- 
nated with  the  sodium  chloride  used  for  "salting  out"  the  soap  in 
the  ordinary  method,  and  it  contains  15  per  cent  by  weight  of  gly- 
cerin against  3  to  4  per  cent  in  the  liquor  obtained  on  direct  saponi- 
fication of  the  fats  or  oils  with  sodium  hydroxide.     The  former 
therefore  effects  a  saving  in  evaporation. 

The  fat  or  oil  is  first  purified  by  steaming  with  I  per  cent  of 
60°  Be,  sulfuric  acid  for  about  two  hours.  It  is  then  transferred 
to  a  wooden  vessel  equipped  with  perforated  steam  pipes,  also  a 
well-fitting  cover  to  exclude  air  which  would  cause  the  fatty  acids 
to  darken,  and  mixed  with  50  per  cent  water  and  1.5  per  cent  of  the 
Twitchell  reagent  The  latter  is  prepared  by  allowing  an  excess  of 
sulfuric  acid  to  act  on  a  solution  of  naphthalene  (or  other  aro- 


392         FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH      XIX 

matic  hydrocarbon)  in  oleic  acid,  which  results  in  the  production 
of  a  body  having  the  general  composition: 


/SOaH 
6< 
X 


CioHe 

Naphthalene-sulf  o-stearic  acid. 

It  is  advisable  to  introduce  a  small  percentage  of  free  fatty  acids 
to  start  the  hydrolysis  which  otherwise  takes  a  little  time  to  begin. 
The  material  is  steamed  for  twenty-four  hours,  whereupon  a  small 
quantity  (o.i  to  0.2  per  cent)  of  60°  Be.  sulfuric  acid  is  added  to 
break  up  the  emulsion  and  permit  the  fatty  acids  to  rise  to  the  sur- 
face and  the  glycerol  to  pass  into  the  aqueous  liquor  below.  About 
0.05  per  cent  of  barium  carbonate  is  finally  added  to  neutralize  the 
mineral  acid. 

The  resulting  fatty  acids  are  dark  in  color  and  must  be  distilled. 
This  is  usually  affected  after  a  preliminary  treatment  with  concen- 
trated sulfuric  acid  as  in  method  (b)  to  increase  the  yield  of  stearin, 
which  is  of  special  importance  when  the  product  is  to  be  used  for 
manufacturing  candles.  The  yield  is  the  same  as  obtained  from 
the  saponification  or  mixed  process  respectively,  depending  upon 
the  exact  method  of  treatment. 

(e]  Hydrolysis  by  Means  of  Ferments.  This  method  is  also 
meeting  with  some  favor,  as  it  produces  a  large  yield  of  glycerin 
uncontaminated  with  salt  or  other  solids  difficult  of  separation. 
Many  soap  manufacturers  accordingly  hydrolyze  their  stock  by 
means  of  ferments  to  separate  the  glycerin,  and  then  saponify  the 
resulting  fatty  acids  with  sodium  carbonate,  either  directly,  or  after 
first  purifying  them  by  steam  distillation. 

The  ferment  is  derived  from  the  castor  plant  by  grinding  the 
decorticated  castor  beans  with  water  and  filtering  through  cloth, 
whereupon  a  white  creamy  filtrate  is  obtained  which  is  set  to  one 
side  and  allowed  to  ferment  spontaneously.  The  ferment  which 
rises  to  the  surface  is  skimmed  off  and  used  while  fresh.  It  is  com- 
posed of  a  thick  creamy  substance  containing  approximately  38  per 
cent  of  fatty  acids  derived  from  castor  oil,  $8  per  cent  of  water  and 
4  per  cent  of  an  albuminoid  substance  containing  the  active  material. 

The  fat  or  oil  to  be  treated  is  mixed  with  40  per  cent  water,  5 
to  8  per  cent  of  the  ferment  and  0.2  per  cent  of  manganese  sulfate 
in  a  lead-lined  vessel  equipped  with  a  steam  coil  and  a  perforated 
compressed-air  pipe.  Heat  is  then  turned  on,  and  the  temperature 
maintained  2  to  3°  C.  above  the  melting-point  of  the  fat  or  oil. 
The  mass  is  agitated  by  air  introduced  through  the  perforated  pipe 
and  the  treatment  continued  one  to  three  days  until  the  hydrolysis 


XIX  FATTY-ACID  PITCH  393 

• 

is  complete.  Sufficient  steam  is  then  turned  on  to  bring  the  mass 
to  a  temperature  of  80  to  85°  C,  whereupon  0.30  to  0.45  per  cent 
of  50  per  cent  of  sulfuric  acid  is  stirred  in  by  air.  This  breaks  up 
the  emulsion,  the  clear  fatty  acids  rising  to  the  top  and  the  aqueous 
liquor  containing  the  glycerin  settling  to  the  bottom. 

When  the  separated  fatty  acids  are  pale  in  color  they  may  be 
saponified  directly  for  manufacturing  soaps.  Where  dark-colored 
fats,  oils  or  greases  have  been  employed,  which  result  in  the  produc- 
tion of  dark-colored  fatty  acids,  the  mass  is  distilled  with  steam, 
whereupon  the  fatty-acid  pitch  is  obtained  as  residue.  Candle  stock 
may  also  be  produced  by  subjecting  the  purified  fatty  acids  to  a  low 
temperature  and  filtering,  as  described  previously. 

It  is,  of  course,  understood  that  when  the  crude  oils  or  fats  (tri- 
glycerides)  or  the  free  fatty  acids  derived  from  them  (by  any  of 
the  foregoing  processes  of  hydrolysis)  are  saponified  directly  with 
sodium  carbonate  (soda  ash),  no  fatty-acid  pitch  is  produced. 

Refining  Vegetable  Oils  by  Means  of  Alkali.  Most  vegetable 
oils  intended  for  edible  purposes,  whether  they  are  to  be  used  for 
salad  oils,  lard  substitutes,  margarine  manufacture,  or  directly  for 
cooking  oils  and  shortening,  are  first  treated  with  caustic  soda  for 
the  purpose  of  removing  free  acids,  coloring  matter,  albuminous 
material,  resins,  etc.  The  oils  chiefly  treated  are  cotton-seed,  corn, 
soya  bean,  cocoanut  and  peanut  oils. 

(a)  Refining  Cotton-seed  Oil.  Crude  cotton-seed  oil  when 
obtained  fresh  from  the  seed  varies  in  color  from  reddish  brown  to 
almost  black.  This  is  due  in  part  to  the  coloring  matter,  which  is 
a  dark  resinous  substance  capable  of  combining  with  caustic  soda, 
forming  a  water-soluble  salt,  also  albumin  and  pectin  bodies.  The 
method  of  refining  the  oil  consists  in  agitating  it  with  varying  quan- 
tities of  caustic  soda  solution,  the  strength  of  which  will  range  from 
i.io  to  i. 20  specific  gravity,  according  to  the  percentage  of  free 
fatty  acids  present  and  the  practice  of  the  individual  refiner.  The 
agitation  is  effected  by  mechanical  stirrers  in  large  tanks  provided 
with  heating  coils.  The  quantity  of  alkaline  liquor  added  is  deter- 
mined by  careful  laboratory  tests  and  run  in  through  perforated 
pipes.  The  effect  of  the  alkali  is  first  to  darken  the  oil  and  appar- 
ently thicken  it.  After  a  short  time  small  flakes  begin  to  separate 
and  heat  is  then  applied.  As  the  temperature  increases,  the  flakes 
become  larger,  owing  to  the  soap  softening  and  running  together. 
When  the  right  point  is  reached,  at  temperatures  varying  from  100 
to  130°  R,  steam  and  agitation  are  shut  off  and  the  soap  drops  to 
the  bottom  of  the  kettle,  forming  a  mucilaginous  mass,  varying  in 


394         FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH      XIX 

* 

color  from  yellow  to  brown,  through  all  shades  of  green  and  red. 
This  material  is  known  as  the  "foots."  The  clear  light  yellow  oil 
which  is  pumped  off  the  foots  is  then  refined  further  for  edible  pur- 
poses. Cotton-seed  oil  purified  in  this  manner  is  known  to  the 
trade  as  "summer  yellow  oil/*  When  used  in  making  lard  substi- 
tutes it  is  bleached  with  fuller's  earth  and  then  deodorized,  gen- 
erally by  the  use  of  steam.  Salad  oil  is  obtained  by  chilling  the 
summer  yellow  oil  s&  as  to  crystallize  out  the  palmitin  which  is 
separated  by  pressing  or  filtering. 

In  the  United  States  alone  the  annual  production  of  cotton-seed 
foots  amounts  to  approximately  half  a  million  barrels.  The  foots 
vary  in  gravity  from  0.97  to  1.04,  averaging  about  i.oo.  They  con- 
tain the  soda  salts  of  the  coloring  matter,  the  soda  soaps  of  any  free 
fatty  acids  present  in  the  cotton-seed  oil  (30  to  45  per  cent),  the 
coagulated  albumin  (8  to  12  per  cent),  phytosteryl,  and  varying 
quantities  of  mechanically  entrained  cotton-seed  oil  (triglycerides). 

Cotton-seed  foots  are  sold  on  the  basis  of  "50  per  cent  fatty 
acid."  As  a  matter  of  fact  they  contain  between  35  and  65  per 
cent,  averaging  about  45  per  cent.  A  representative  sample  con- 
tained :  * 

Fatty  anhydrides  (corresponding  to  a  "5o-per  cent  soap  stock")  48. 50  per  cent 

Glycerin 3-98  per  cent 

Caustic  soda  (NaaO). 3- 20  per  cent 

Foreign  organic  matter 5- 9°  per  cent 

Coloring  matter 2.41  per  cent 

Water 36.00  per  cent 

Total * 100. oo  per  cent 

The  cotton-seed  foots  may  be  converted  directly  into  soap  by 
boiling  up  with  a  small  excess  of  caustic  soda  and  "salting"  it  put 
in  the  usual  manner,  when  no  pitch  will  be  obtained.  The  resulting 
soap  is  known  as  "killed  foots"  and  the  dark  lye  containing  the 
coloring  matter  and  impurities  are  run  to  waste.  A  process  has  also 
been  described  for  recovering  a  shellac-like  substance  from  cotton- 
seed foots  by  oxidizing  with  hydrogen  peroxide  in  an  alkaline  solu- 
tion and  acidifying  to  separate  the  fatty  matter.5 

Usually,  however,  the  cotton-seed  foots  are  subjected  to  distilla- 
tion. They  are  first  boiled  with  sufficient  alkali  to  complete  the 
saponification  and  then  treated  with  mineral  acid  to  liberate  the 
fatty  acids.  Or  the  foots  may  be  acidified  while  hot  with  dilute 
sulfuric  acid,  whereupon  a  "black  grease"  containing  about  90  per 
cent  of  the  total  fatty  acids  (calculated  as  oleic)  rises  to  the  sur- 
face. This  is  separated  and  subjected  to  the  Twitchell  or  other 
hydrolyzing  processes  to  break  up  any  neutral  fat  and  recover  all 


XIX  FATTY-ACID  PITCH  395 

the  glycerin.    The  fatty  acids  obtained  in  this  manner  are  equiva- 
lent to  7,5  to  8.5  per  cent  of  the  original  weight  of  the  cotton-seed 

011  used.     They  are  subjected  to  vacuum  distillation  with  super- 
heated steam  to  separate  the  pure  fatty  acids  from  the  residue  of 
fatty-acid  pitch,  variously  called  "cotton  pitch,"  "cotton-oil  pitch/' 
" cotton-seed-oil  pitch,"  "cotton-stearin  pitch,"  "cotton-seed-oil-foots 
pitch,"  etc.    The  quantity  of  pitch  produced  will  range  between  10 
and  20  per  cent  of  the  weight  of  the  crude  fatty  acids   (black 
grease)  distilled,  which  is  equivalent  to  i  to  2  per  cent  by  weight 
of  the  original  cotton-seed  oil.     The  yield  will  depend  upon  the 
degree  the  oil  is  saponified,  the  amount  of  impurities  present,  the 
efficiency  of  the  distilling  apparatus  and  the  extent  to  which  the  dis- 
tillation is  carried.    The  still  generally  used  holds  3  to  5  tons  and 
the  distillation  is  conducted  intermittently.    Two  types  of  conden- 
sers are  used,  viz.:  (i)  water-cooled  and  (2)  air-cooled.     From 
these  the  vapors  are  passed  through  another  condenser  in  which  a 
water  spray  removes  the  lower  fatty  acids.    Any  volatile  fatty  acids 
distil  over  first,  followed  by  the  free  fatty  acids  of  higher  boiling- 
points.    The  decomposition  of  any  neutral  fat  present  into  unsat- 
urated  hydrocarbons  and  unsaturated  fatty  acids  does  not  com- 
mence until  the  concentration  of  the  neutral  fat  in  the  still  reaches 

12  to  15  per  cent 

The  purified  fatty  acids  recovered  by  distillation  are  used  for 
manufacturing  soaps.  The  fatty-acid  pitch  is  usually  soft  in  con- 
sistency, moderately  stringy  and  of  a  pale  brown  color  when  exam- 
ined by  transmitted  light  in  thin  layers. 

(b)  Refining  Corn  Oil.  Corn  oil  is  sometimes  refined  by  treat- 
ing with  a  small  proportion  of  caustic  soda  in  a  manner  similar  to 
the  method  described  for  cotton-seed  oil.  Upon  deodorizing  the  re- 
fined product  with  superheated  steam  under  reduced  pressure,  while 
heated  to  a  temperature  of  400°  F,,  an  edible  product  is  obtained, 
used  as  a  salad  oil,  also  for  cake  and  biscuit  making.  It  may  also 
be  converted  into  a  lard  compound  by  a  hydrogenation  process. 
The  corn-oil  foots  are  treated  by  a  method  similar  to  the  one  used 
for  refining  cotton-seed  foots.  A  pitch  is  obtained  known  as  "corn- 
oil  pitch,"  possessing  a  comparatively  high  fusing-point,  character- 
ized by  its  rubber-like  properties  and  lack  of  ductility.  If  the  dis- 
tillation is  carried  too  far,  the  pitch  will  actually  solidify  in  the  still 
and  can  only  be  removed  with  great  difficulty. 

Refining  Refuse  Greases,  (a)  Refining  Packing-house  and 
Carcass-rendering  Greases.  "Tallow"  is  the  name  applied  to  the 
purified  solid  fat  or  "suet"  obtained  from  cattle.  It  is  used  ex- 
tensively for  producing  soap  and  candle  stock.  The  crude  fat  is 
first  "rendered"  by  boiling  with  water  in  an  open  vessel  to  separate 


396         FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

it  from  any  albuminous  matter  or  other  impurities  present,  and  then 
clarified  by  washing  with  weak  brine.  "Lard"  is  obtained  by  ren- 
dering the  soft  fats  which  surround  the  kidneys,  intestines  and  backs 
of  pigs.  Tallow  and  lard  may  be  used  as  such  for  manufacturing 
soaps,  but  for  producing  candles  they  must  first  be  hydrolyzed  and 
purified  by  steam-distillation. 

The  waste  meat  scraps  obtained  from  packing  houses,  also  the 
carcasses  of  animals  freed  from  the  bones,  are  treated  with  steam  in 
large  digestors  at  a  high  pressure  to  separate  the  fat.  When  the 
cooking  is  complete,  the  batch  is  allowed  to  stand  quietly  to  permit 
the  grease  to  rise  to  the  surface  and  the  disintegrated  meat-fibers 
to  settle.  The  grease  is  skimmed  off  and  mixed  with  any  additional 
grease  recovered  from  the  settlings  by  filter-pressing.  The  residue 
is  then  converted  into  fertilizer,  and  the  aqueous  liquid  used  for 
making  glue.  The  grease  recovered  from  this  process  has  a  dis- 
agreeable odor  and  a  dark  color,  and  must  be  hydrolyzed  and  steam- 
distilled  before  it  can  be  used  for  manufacturing  either  candles  or 
soap.  The  residue  from  the  steam  distillation  process,  amounting 
to  between  5  and  6  per  cent  of  the  grease,  constitutes  a  variety  of 
fatty-acid  pitch  having  a  light  brown  color  when  viewed  in  a  thin 
layer  and  great  ductility  (unless  the  pitch  is  distilled  too  far).  A 
packing-house  grease  has  been  extensively  marketed  in  this  country 
under  the  name  of  "yellow  grease." 

(b)  Refining  Bone  Grease.  The  bones  recovered  from  pack- 
ing houses  or  carcass-rendering  works  are  used  for  manufacturing 
glue,  bone-black  (used  for  decolorizing  petroleum  distillates),  and 
fertilizer.  Bones  from  the  head,  ribs  and  shoulder-blades  contain 
12  to  13  per  cent  of  fat,  whereas  the  large  thigh  bones  ("mar- 
rows") contain  20  per  cent.  The  fat  is  extracted  by  breaking  up 
the  bones  into  small  fragments  and  then  either: 

1 i )  Treating  with  steam  in  an  autoclave  under  a  pressure  of 
2  to  3  atmospheres,  whereupon  a  portion  of  the  fat  separates  and 
floats  to  the  surface,  the  gelatin  or  glue  goes  into  solution,  and  the 
mineral  ingredients   (calcium  phosphate,  etc.)   remain  as  residue. 
From  8  to  9  per  cent  of  fat  (based  on  the  dry  weight  of  the  bones) 
is  recovered  in  this  manner. 

(2)  Extracting  the  dried  bones  with  a  volatile  solvent  such  as 
naphtha,  carbon  tetrachloride,  or  benzol  in  a  suitable  apparatus. .  A 
much  higher  percentage  of  fat  is  extracted  in  this  manner,  but  the 
cost  of  operation  is  higher,  due  to  unavoidable  losses  of  solvent,  and 
the  odor  of  the  product  is  very  strong. 

In  either  event  the  extracted  bone  fat  is  first  hydrolyzed  by  any 
of  the  foregoing  methods  and  then  steam-distilled,  whereupon  a 
variety  of  fatty-acid  pitch,  known  as  "bone-fat  pitch,"  is  recovered 
as  residue,  amounting  to  5  to  6  per  cent  by  weight  of  the  bone-fat. 


XIX  FATTY-ACID  PITCH  397 

The  product  may  be  used  for  manufacturing  soap,  or  after  cooling 
and  filtering,  the  "stearin"  may  be  converted  into  candles,  and  the 
"olein"  either  used  for  manufacturing  soap  or  else  marketed  as 
such  for  "wool  oils." 

(c)  Refining  Garbage  and  Sewage  Greases.     The  average  city 
garbage  as  collected  contains : 

Water 70-80  per  cent 

Grease 3-  4  per  cent 

Tankage 10-20  per  cent 

Tailings  (rubbish) , 3-  6  per  cent 

.  It  is  treated  in  a  manner  similar  to  that  used  for  working  up  the 
refuse  from  packing  houses  and  carcass-rendering  establishments, 
namely  by  boiling  in  large  digesters  holding  8  tons  for  six  hours 
under  a  pressure  of  70  to  80  Ib.  (Arnold-Egerton  System),6  This 
reduces  the  material  to  a  pulpy  mass,  which  is  filter-pressed  to  re- 
move the  water  and  grease.  The  residue,  known  as  "tankage,"  is 
dried  and  ground  for  use  as  fertilizer.  The  filtrate  is  allowed  to 
stand,  whereupon  the  grease  rises  to  the  surface  and  is  skimmed  off. 
The  grease,  when  dehydrated,  has  a  dark  brown  color.  It  is  hydro- 
lyzed  to  separate  the  glycerin,  and  the  resulting  fatty  acids  purified 
by  steam-distillation  to  render  them  suitable  for  manufacturing  soaps 
and  candles.  The  residue,  known  as  "garbage  pitch,"  amounting 
to  5  to  7  per  cent  by  weight  of  the  garbage,  has  a  dark  color  when 
viewed  in  a  thin  layer,  and  is  quite  susceptible  to  temperature 
changes. 

Sewage  also  carries  a  proportion  of  grease  which  is  now  often 
being  recovered,  especially  in  large  cities.  The  sewage  is  first  run 
into  large  tanks,  where  the  solid  matter  known  as  "sludge"  settles 
to  the  bottom.  The  precipitation  may  be  accelerated  by  adding  a 
small  percentage  of  slaked  lime.  After  drawing  off  the  liquor,  the 
sludge  is  treated  with  a  small  quantity  of  sulruric  acid  to  break 
up  any  insoluble  soaps,  and  then  boiled  in  large  digestors  under 
pressure  to  hydrolyze  the  fats,  and  enable  the  grease  to  separate. 
The  residue  is  dried  and  used  as  fertilizer.  The  grease  is  dehy- 
drated, then  hydrolyzed  and  finally  distilled  with  superheated  steam, 
yielding  about  25  per  cent  of  a  fatty-acid  pitch  known  as  "sewage 
pitch."  The  characteristics  of  this  are  similar  to  those  of  garbage 
pitch.  The  distillate  contains  about  50  per  cent  of  liquid  olein  and 
50  per  cent  of  solid  stearin  melting  at  about  113°  F.7 

(d)  Refining  Woolen-mill  Waste.     Olive  oil,  lard  oil,  neat's- 
foot  oil,  saponification  olein  (or  saponified  olein)  and  distillation 
olein  (or  distilled  olein)  are  sold  under  the  names  "wool  oils"  or 
"cloth  oils,"  and  used  in  woolen  mills  for  lubricating  the  wool  be- 
fore spinning  into  yarn,  or  for  oiling  old  woolen  rags  before  grind- 


398         FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

ing  and  "pulling**  in  the  manufacture  of  "shoddy/'  One  of  the 
perquisites  of  the  wool  oils  is  that  they  shall  have  no  tendency  to 
dry  or  oxidize,  and  they  must  also  be  easily  removable  on  boiling 
the  finished  woolen  goods  or  shoddy  with  a  solution  of  soap  or  so- 
dium carbonate.  The  presence  of  hydrocarbons,  even  in  small  quan- 
tities, is  objectionable,  as  they  tend  to  prevent  the  removal  of  the 
wool  oils  during  the  scouring  process. 

After  the  goods  are  scoured,  the  liquid  is  mixed  with  freshly 
slaked  lime  which  serves  to  precipitate  the  soaps.  The  curds  are 
settled  out  and  separated,  then  acidified  with  dilute  sulfuric  acid 
to  separate  the  free  fatty  acids,  which  are  skimmed  off  and  filtered 
to  remove  any  dirt.  The  product  known  as  "fuller's  grease,"  "seek 
oil,"  or  "magma  oil/*  is  distilled  with  steam,  whereby  the  wool  oils 
are  recovered,  and  a  residue  of  fatty-acid  pitch  obtained,  amounting 
to  to  per  cent  by  weight  of  the  grease;  known  as  "fuller's-grease 
pitch,"  or  "seek-oil  pitch."  This  will  vary  in  its  properties  depend- 
ing upon  the  raw  materials  entering  into  the  composition  of  the 
original  wool  oils. 

Treatment  of  Wool  Grease.  Wool  grease,  known  also  as 
"wool  wax,"  or  "wool  degras,"  represents  the  oily  material  natur- 
ally present  in  sheep's  wool,  and  differs  entirely  from  the  so-called 
"wool  oil"  discussed  previously.  Wool  grease  is  in  reality  an  ani- 
mal wax,  as  it  contains  no  glycerin  or  glycerides  whatsoever.  It  is 
extracted  by  boiling  the  cut  wool  with  an  alkaline  soap  solution  or 
sodium  carbonate.  Formerly,  volatile  solvents  were  used  for  this 
purpose,  but  the  method  is  no  longer  practiced.  After  boiling  with 
soap  or  sodium  carbonate,  the  liquor  is  acidified  with  sulfuric  acid, 
whereupon  grease  rises  to  the  surface  and  is  skimmed  off.  Dehy- 
drated wool  grease  melts  between  86  and  104°  F.  and  contains  ap- 
proximately 55-60  per  cent  fatty  acids,  also  40-45  per  cent  higher 
alcohols  ( unsaponifiable ) . 

Wool  grease  is  treated  in  various  ways,  and  among  others  by  a 
direct  process  of  distillation  with  superheated  steam  without  pre- 
vious hydrolysis  (as  the  waxes  present  are  not  amenable  to  such 
treatment)  whereby  the  following  reactions  take  place:8  (i)  dis- 
tillation of  the  free  fatty  acids,  which  continues  up  to  one-third  of 
the  distillate;  (2)  decomposition  of  free  hydroxy  acids  principally 
into  lactones,  some  of  which  distil  over  and  some  decomposing  into 
carbon  dioxide  and  solid  unsaturated  acids;  (3)  decomposition  of 
neutral  esters  into  unsaturated  acids  and  unsaturated  hydrocarbons. 


XIX  FATTY-ACID  PITCH  398 

Since  wool  grease  contains  an  average  of  65  per  cent  esters,  this 
will  account  for  the  high  percentage  of  unsaponifiable  matter  in 
wool  grease  products ;  (4)  distillation  of  hydrocarbons.  About  39 
per  cent  of  the  total  fatty  acids  in  wool  grease  is  oxidized  acids,  and 
of  these  about  25  per  cent  work  their  way  into  the  distillate  and  the 
remainder  are  found  in  the  residual  pitch.  The  pitch  consists  of 
about  85  per  cent  polymerized  hydrocarbons  and  12  to  15  per  cent 
fatty  acids  (of  which  40  to  65  per  cent  are  oxidized  acids).  The 
course  of  the  treatment  is  shown  in  Table  XXVII.  The  residue  of 
fatty-acid  pitch  is  known  as  "wool-grease  pitch,"  "wool-fat  pitch," 
"wool  pitch,"  or  "cholesterol  pitch."  The  olein  (known  as  "dis- 
tilled-grease  olein"  or  "degras  oil"),  is  used  as  a  leather  or  wool 
oil,  and  the  stearin  (known  as  "degras  stearin"),  is  used  in  the 
soap  industry  or  as  a  leather  "stuffing  grease." 

TABLE  XXVII 

Wool  Grease 
(distilled) 


Gas  oil 
(distilled  or 
marketed) 

Pale  distillate 
(cold  pressed) 

4                                        4 
Back  ends                                 Pitch 
(distilled  01                            (left  in  the 
marketed)                                 still) 

1 
Olein 
(redistilled) 

1       - 
(cold  pressed) 

(he 

4 
Stearin 
t  pressed)    or    (redistilled) 

(cold  pressed,  then 
hot  pressed) 

4 
Pale  olein 
(marketed) 

4                           i 
Stearin                      Stearin       1 
(marketed)                 (marketed) 

i               i 

Hot-pressed            4                    4 
Olein            Hot-pressed      Stearin 
(marketed             Olein         (marketed) 
or  redis-          (marketed 
tilled)              or  redis* 
tilled) 

Physical  and  Chemical  Properties  of  Fatty-acid  Pitches. 
Fatty-acid  pitches  vary  considerably  in  their  physical  and  chemical 
properties,  depending  upon  the  following  circumstances : 9 

1 i )  The  nature  of  the  fat  or  oil  from  which  the  fatty  acids  are 
derived.     If  these  contain  low  melting-point  fatty  acids,  the  fatty- 
acid  pitch  will  be  soft  in  consistency,  provided  the  distillation  has 
not  been  carried  too  far.    On  the  other  hand,  if  high  melting-point 
fatty  acids  predominate,  the  fatty-acid  pitch  will  be  semi-solid  to 
solid  in  consistency. 

(2)  The  proportion  of  neutral  fats  or  oils  present  in  the  fatty- 


400         FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

acid  mixture,  which  will  prove  substantial  if  the  process  of  hy- 
drolysis is  not  carried  to  theoretical  completion.  Since  the  neutral 
fats  or  oils  (triglycerides)  do  not  distil  with  superheated  steam, 
they  concentrate  in  the  fatty-acid  pitch,  and  are  very  apt  to  decom- 
pose into  hydrocarbons  (unsaponifiable)  if  the  distillation  is  carried 
too  far.  If  the  distillation  is  stopped  at  a  point  without  decom- 
posing the  neutral  fats  or  oils,  the  value  of  the  fatty-acid  pitch  is 
enhanced  by  their  presence,  as  they  are  more  stable  and  weather- 
resistant  than  the  fatty  acids  themselves. 

(3)  The  extent  to  which  the  distillation  is  carried  and  the 
temperature  at  which  it  is  performed.  If  distilled  too  far  or  at  too 
high  a  temperature,  the  fatty  acids  decompose  in  the  presence  of 
steam,  first  into  hydroxy  acids,  which  in  turn  break  down  into  lac- 
tides,  unsaturated  products  and  lactones  in  the  following  manner: 

(a)  «-hydroxy  acids  are  converted  into  lactides. 

(b)  jS-hydroxy    acids    become    converted    into    unsaturated 
products. 

(c)  y  and  8  hydroxy  acids  are  transposed  into  cyclic  esters  of 
the  nature  of  y  and  8  lactones  respectively. 

It  follows,  therefore,  that  the  fatty-acid  pitches  contain  free 
fatty  acids  (mostly  polymerized),  their  lactones  (anhydrides),  un- 
decomposed  glycerides  (neutral  fats  or  oils),  condensation  products 
of  unknown  composition,  hydrocarbon  decomposition  products,  and 
in  the  case  of  fatty-acid  pitches  derived  from  wool  grease,  we  find 
cholesterol  and  higher  alcohols.10  Their  cryoscopic  molecular 
weights  vary  from  370  to  680,  and  the  so-called  "rubber  pitches" 
show  the  highest  molecular  weights  and  contain  up  to  80  per  cent 
saponifiable  matter. 

The  presence  of  hydrocarbon  decomposition  products  is  evi- 
denced largely  by  the  color  of  the  pitch  when  examined  in  a  thin 
layer.  If  these  are  present,  the  pitch  will  be  a  black,  otherwise  it 
will  have  a  rich  brown  color.  The  percentage  of  saponifiable  con- 
stituents present  in  the  fatty-acid  pitch  is  a  criterion  of  its  quality. 
The  larger  the  percentage,  the  better  will  be  the  quality  from  the 
standpoint  of  weather-resistance.  Fatty-acid  pitches  of  the  opti- 
mum quality  contain  not  less  than  90  per  cent  of  saponifiable  con- 
stituents. They  are  as  weather  resistant  as  any  bituminous  sub- 
3tance.  The  smaller  the  percentage  of  saponifiable  constituents  in 
the  pitch,  the  less  weather-resistant  it  will  prove  to  be. 

In  recent  years  there  has  been  a  tendency  to  remove  more  and 


XIX  FATTY-ACID  PITCH  401 

more  of  the  saponifiable  ingredients  from  the  fatty-acid  pitches,  in 
view  of  the  high  price  commanded  by  the  fatty  acids,  and  also  be- 
cause of  improvements  effected  in  the  distillation  process.  The 
author  has  examined  fatty-acid  pitches  containing  as  high  as  98 
per  cent  unsaponifiable  constituents.  These  appear  glossy  black  in 
color  and  almost  opaque  in  a  thin  layer,  and  therefore  find  a  ready 
use  in  the  manufacture  of  cheap  lacquers  and  japans,  not  intended 
for  exposure  out  of  doors. 

All  fatty-acid  pitches  are  converted  in  a  more  or  less  infusible 
and  insoluble  mass  upon  exposure  to  the  weather  for  a  long  period, 
or  upon  heating  a  short  time  to  a  temperature  of  250  to  350°  C.  in 
contact  with  air.11  This  is  equally  true  whether  or  not  unsaponifi- 
able constituents  are  present,  and  makes  this  class  of  pitches  espe- 
cially valuable  for  manufacturing,  baking  japans  and  varnishes.12 
They  may  also  be  hardened,  or  converted  into  insoluble  and  infusible 
substances  by  heating  with  sulfur,13  or  with  sulfur  and  an  alkaline 
"accelerator"  (e.  g.,  thiocarbanilide  or  diphenylguanidine ) ,14  or  by 
heating  a  mixture  of  fatty-acid  pitch  and  phenol  or  cresol  with 
sulfur  dichloride  or  selenium  monochloride,15  or  by  heating  a  mix- 
ture of  fatty-acid  pitch  and  phenol  or  cresol  with  formaldehyde  or 
hexamethylenetetramine  which  results  in  the  formation  of  a  hard 
resinous  condensation  product.16 

Various  methods  have  been  proposed  for  blowing  fatty-acid 
pitches,  including:  blowing  wool-fat  pitch  with  air  at  an  elevated 
temperature;17  blowing  a  mixture  of  fatty-acid  pitch  and  montan 
wax,  with  or  without  the  addition  of  colored  mineral  pigments;18 
etc.  Blowing  with  air  at  elevated  temperatures  rapidly  increases 
their  fusing-point  and  at  the  same  time  tends  to  convert  them  into 
the  insoluble  modification.10 

The  insoluble  (polymerized)  form  of  fatty-acid  pitch  may  again 
be  rendered  soluble  in  organic  solvents  by  a  process  of  mechanical 
mixing  (i.  e.,  "hot-rolling")  with  natural  resins,  resin  esters,  or  syn- 
thetic resins.20 

A  highly  elastic  form,  termed  "rubber  pitch/'  is  obtained  by 
heating  soft  fatty-acid  pitch  to  240-250°  C.,  with  10  per  cent  of 
either  sulfuric  or  nitric  acid,21  and  the  resultant  product  is  charac- 
terized by  being  extremely  resistant  to  temperature  changes,  ap- 
proaching vulcanized  rubber  in  its  physical  properties.  Soft  pitches 


402         FATTY- ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

may  also  be  hardened  by  heating  with  oxides  of  magnesium,  man- 
ganese or  lead ;  lime,22  picric  acid,28  etc. 

Fatty-acid  pitches  containing  a  large  proportion  of  saponifiable 
constituents  show  an  extremely  low  susceptibility  index,  in  fact  lower 
than  any  other  class  of  bituminous  materials.  Conversely  fatty- 
acid  pitches  in  which  the  unsaponifiable  constituents  predominate 
are  apt  to  have  quite  a  high  susceptibility  index. 

In  general,  the  various  classes  of  fatty-acid  pitch  are  character- 
ized by  the  following  predominating  physical  properties,  assuming 
that  they  have  been  carefully  prepared  and  neither  overheated  nor 
distilled  too  far,  viz. : 

Fatty-acid  pitches  made  from  lard  are  usually  very  ductile  with  a 

low  susceptibility  index. 
Fatty-acid  pitches  made  from  tallow  are  generally  hard,  lacking  in 

auctility  with  a  low  susceptibility  index. 
Palm  oil  pitches  are  hard,  lacking  in  ductility  with  a  moderately 

high  susceptibility  index. 
Cotton-seed-foots  pitch  is  usually  soft,  of  moderate  ductility  having 

a  low  susceptibility  index. 
Corn-oil-foots  pitch  is  extremely  rubbery,  shows  little  ductility  and 

has  an  extremely  low  susceptibility  index. 

Packing-house  pitch  is  ductile  and  has  a  low  susceptibility  index. 
Bone-fat  pitch  lacks  ductility  and  has  a  moderately  high  suscepti- 
bility index.    Its  color  in  a  thin  layer  and  streak  are  black. 
Garbage  and  sewage  pitches  are  ductile  with  a  high  susceptibility 

index.  Their  color  in  a  thin  layer  and  streak  are  usually  black. 
Wool-grease  pitch  is  ductile  and  has  an  extremely  high  susceptibility 

index.    Its  color  in  a  thin  layer  and  streak  are  usually  black. 

Fatty-acid  pitches  (referring  to  all  types)  comply  with  the  fol- 
lowing characteristics : 

(Test    i)    Color  in  mass Dark  brown  to  black 

(Test    la)  Homogeneity  to  the  eye  at  77°  F. , Uniform  to  gritty 

(Test   a£)  Homogeneity  under  miscroscope Uniform  to  lumpy 

(Test  3)    Appearance  surface  aged  indoors  one  week.  Bright 

(Test   4)    Fracture None  to  conchoidal 

(Test   5)    Lustre Bright 

(Test   6)    Streak  on  porcelain Light  yellow,  brown  to  black 

(Test   7)    Specific  gravity  at  77°  F 0.90-1 . 10 

(Test   9*)  Penetration  at  77°  F , 8  to  above  360 

(Test   9*)  Consistency  at  77°  F 0-40 

(Test   9</)  Susceptibility  index, f 8-40 

(Test  10)    Ductility Variable 


XIX  FATTT-ACID  PITCH  403 

(Test  154)  Fusing-pojnt  (K*  and  S.  method) 35-225°  F. 

(Test  15^)  Fusing-point  (R.  and  B.  method) 50-245°  F. 

(Test  16)     Volatile  matter  500°  F.,  5  hours o.  5-7. 5  per  cent  (Set  Note) 

(Test  17*)  Flash-point     450-650°  F. 

(Test  19)     Fixed  carbon 5-  35  per  cent 

(Test  21)     Solubility  in  carbon  disulfide 95-100  per  cent 

Non-mineral  matter  insoluble o-    5  per  cent 

Mineral  matter o-    5  per  cent 

(Test  22)     Carbenes o-    5  per  cent 

(Test  23)     Solubility  in  88°  petroleum  naphtha 80-100  per  cent 

(Test  28)     Sulfur o  per  cent 

(Test  30)     Oxygen 2-  10  per  cent 

(Test  33)     Solid  paraffins Trace 

(Test  340)  Saturated  hydrocarbons o-    5  per  cent 

(Test  34^)  Sulfonation  residue o-    5  per  cent 

(Test  370)  Acid  value  (including  lactone  value) 2-100 

(Test  37<r)   Ester  value , , 40-125 

(Test  37  d)  Saponification  value 60-200 

(Test  37?)    Saponifiable  constituents 5~  98  per  cent 

Unsaponifiable  constituents 2-95  per  cent 

(Test  37/)   Hydrocarbons  in  unsapomfiable  matter. . .   90-100  per  cent 

Higher  alcohols  (cholesterol)  in  unsaponi- 

fiable  matter o-io  per  cent 

(Test  37^)  Glycerol Tr.-2. 5  per  cent 

(Test  39)     Diazo  reaction No 

(Test  40)     Anthraquinone  reaction No 

(Test  41)    Liebermann-Storch  reaction Yes  in  the  case  of  the  wool 

grease  pitches  only 

NOTB.  In  nearly  all  cases,  a  skin  will  form  over  the  surface  of  the  pitch  during  the  determination  of  the  volatile 
matter.  This  is  characteristic.  Certain  fatty-acid  pitches,  especially  those  containing  a  large  percentage  of 
saponifiable  constituents,  often  toughen  up  and  solidify  to  a  rubber-like  mass  during  this  test, 

Table  XXVIII  contains  the  results  of  the  examination  of  repre- 
sentative samples  of  fatty-acid  pitch  by  the  author. 

According  to  Julius  Marcusson 24  the  saponification  value  of 
fatty-acid  pitches  ranges  from  24  to  106,  whereas  the  saponification 
value  of  petroleum  asphalts  does  not  exceed  21.  Lukens  2C  reports 
that  the  saponification  value  of  fatty-acid  pitches  ranges  from  45  to 
100  and  of  petroleum  asphalts  from  5  to  18. 

Fatty-acid  pitches  may  be  distinguished  from  asphalts  by  the 
small  percentages  of  sulfonation  residue  and  sulfur.  Marcusson 
contends  that  fatty-acid  pitches  contain  a  trace  of  sulfur  compounds, 
derived  from  impurities  present  in  the  original  fats  and  also  from 
the  sulfuric  acid  used  for  hydrolysis.  Such  sulfur  compounds  are 
distinguished  from  those  occurring  in  asphalts  by  the  fact  that  they 
-are  not  precipitated  by  mercuric  bromide  (Test  28).  It  is  also 
interesting  to  note  in  this  connection  that  no  such  precipitate  is  ob- 
tained from  fatty-acid  pitches  that  have  been  vulcanized  with  sulfur. 


404 


FATTY-ACID  PITCH 


XIX 


TABLE  XXVIII.— CHARACTERISTICS 


No. 

Test 

From  Lard 

From 
Tallow 

From 
Packing- 
house 
Refuse 

2fl 

ab 
3 
4 
5 
6 
7 

Physical  Characteristics: 
Homogeneity  to  eye  at  77°  F.  

Homo. 
Homo. 
Bright 

Homo. 
Homo. 
Bright 

Homo. 
Lumpy 
Bright 

Homo. 
Homo. 
Bright 

Homo. 
Homo. 
Bright 
Conch. 
Bright 
Brown 
i  060 

Homo. 
Homo. 
Bright    , 

Homogeneity  under  microscope.  

Appearance  surface  aged  seven  days  — 
Fracture  .  

Streak  

Yellow 
0.972 

Yellow 
0.980 

Yellow 
0.990 

Brown 

1,000 

Brown 
1.003 

Specific  gravity  at  77°  F    

9* 
9<? 

9<* 
xofr 

ii 

Mechanical  Tests; 
Penetration  at  115°  F  

Soft 
Soft 
88 
o.o 
0.7 

8.2 

18.3 

0 

42 

75 

0.0 

o.o 
o  75 

Soft 
Soft 
85 

O  0 

1.3 

9-8 
16.7 

0 

36 
88 
o.o 
0.05 
o  9S 

Soft 
280 
83 
o.o 
2.4 

10.  0 

14.3 

IO 

25.5 
27 

0.0 

0.05 
i  75 

22O 

99 

69 

1.5 

5  8 

IS    2 
12.  S 

2-5 

28  S 
18 
o  05 

O.2O 

2    35 

36 

21 

16 
ii.  3 

23    2 
52.0 
22    3 

18  5 
4 
o 
1-75 
3  10 
6  2 

Soft 

IOO 

68 
0.6 
6  3 
15-7 
15-6 
23 
81  5    * 
20 
o.o 
o  40 

3.25 

Penetration  at  77°  F  

Penetration  at  32°  T     

Consistency  at  115°  F      .    

Consistency  at  77°  F  

Consistency  at  32°  F  

Ductility  in  cms.  at  115°  F  

Ductility  in  cms.  at  77°  F  

Ductility  in  cms.  at  32°  F  

Tensile  strength  in  kg.  at  115°  F  

Tensile  strength  in  kg.  at  77°  F  

Tensile  strength  in  kg.  at  32°  F  

150 
IS* 

16 

i?a 
19 

Thermal  Tests: 
Fusing-point,  deg.  F.  (K.  and  S.  method) 
Fusing-point,  deg.F.  (R.  and  B.  method) 
Volatile  500°  F.  in  5  hours,  per  cent.  .  .  . 

44-  S 
57 

2.6 

Little 
Change 
452 

6.2 

59 
74 
3  o 
Little 
Change 
525 

II.  2 

70 
85 
5-3 

Gelat. 

485.5 
10  4 

110 
130 

5-0 
Little 
Change 
486 

12.0 

182 
202 

1.2 

Little 
Change 
482 

18.4 

97 
115 
1.7 
Little 
Change 
Sio 

12.6 

Flash-point  deg.  F    

Fixed  carbon  per  cent  

21 
22 

33 

Solubility  Tests: 
Soluble  in  carbon  disulfide  

IOO.O 

o.o 

0.4 

0.0 
IOO  O 

IOO.O 
0.0 

1-4 

0.0 
IOO.O 

99-7 
0.3 
1.5 
o.o 

IOO.O 

IOO.O 
O.O 

0.5 
0.0 

98.0 

98.5 

2.1 
1.3 
O.I 

86.7 

IOO.O 

o.o 

2.O 

o  o 

IOO.O 

Non-mineral  matter  insoluble.  .......... 

Carbenes  

Soluble  in  88°  petroleum  naphtha  

98 

33 
34* 
37* 
37* 
37* 
37<* 
S7« 
37/ 
37/ 
37* 

Chemical  Tests 
Sulfur           

o.o 

Solid  paraffins  *  ... 

0.0 

o.o 
17.6 

63.  2  \ 

86.  4  / 
167.2 
0.5 

o.o 
0.3 
65.0 

79-8 

144-8 
5-5 
95-0 
5-0 

o.o 

0.0 

63.3 

75.9 
139.2 

1.5 

o.o 

o.o 

o.o 

3.7 
23.5 

74.1 

97-6 
5-0 

Sulf  onation  residue                        •   * 

Acid  value  .  ,  

81.95 
97.55 
179.5 

I.O 

44.1 

112.  0 

I56.I 
15.2 

97.0 
3.0 
o.o 

Lactone  value  

Ester  value  '.  «  *  ... 

Saponification  value.  *  

Unsaponifiable  matter  ,..,... 

Hydrocarbons  In  unsaponifiable  matter.  . 
Higher  alcohols  in  unsaponifiable  matter. 

XIX  FATTY-ACID  PITCH 

OF  TYPICAL  FATTY-ACID  PITCHES 


405 


f 

From 

From 
Bone-fat 

From 
Garbage 

From 
Sewage 

From 
Cottonseed-oil 
Foots 

Corn- 
Oil 
Foots 

From 
Palm-oil 

From 
Wool- 
grease 

Homo. 

* 
Homo. 

Gritty 

Homo. 

Homo. 

Gritty 

Homo. 

Homo. 

Gritty 

Gritty 

Gritty 

Lumpy 

Lumpy 

Homo. 

Lumpy 

Homo. 

Gritty 

Lumpy 

Bright 

Bright 

Bright 

Bright 

Bright 

Bright 

Dull 

Bright 

Bright 

Conch. 

Conch, 

SI.  dull 

Bright 

Black 

Black 

Black 

Yellow 

Brown 

Brown 

Brown 

Black 

Black 

1.036 

i  063 

i.  or  i 

0.992 

0-955 

o  998 

1.042 

1.087 

1.020 

ISO 

145 

130 

Soft 

260 

61 

46 

35 

Soft 

76 

50 

14 

200 

120 

34 

19 

10 

150 

r4 

12 

18 

72 

66 

46 

14 

5 

34 

2.4 

2.6 

2.9 

o.o 

i.i 

7  2 

9  3 

11.  7 

o.o 

7-9 

II.7 

30.0 

2.7 

5-1 

15.8 

24.7 

35-2 

4.2 

55-4 

60.  1 

48.3 

14.1 

I6.5 

25.1 

56.5 

82  o 

32,8 

41.9 

40  5 

33-9 

19.7 

15-3 

8.5 

29-5 

41.0 

35.8 

18 

72-5 

52 

8.5 

31 

5 

35-5 

25 

15 

s 

60 

15 

19 

26,5 

2 

2 

0.5 

47-5 

o 

0 

o.S 

28.5 

10 

0.5 

0 

o 

31 

0.05 

0.50 

0.25 

o  o 

o  05 

0.75 

I.OO 

2.20 

o.o 

o  30 

1.25 

I    10 

O.IO 

o.S 

1-55 

2.2 

5.00 

0.25 

4  ?o 

6    2 

8.0 

a  30 

4.2 

5-4 

9-5 

11.25 

1.05 

126.5 

142 

134 

71.5 

JOI 

210 

161.5 

172 

91.5 

144 

162 

I5I.5 

92 

120 

235  5 

186 

193 

1  08  5 

o  5 

0.6 

0.55 

4.2 

0.38 

0.25 

3-5 

1.2 

7.2 

Little 
Change 

Little 
Change 

Gelat. 

Gelat. 

Gelat. 

Gelat. 

Much 
Change 

Little 
Change 

Little 
Change 

575 

590 

540 

635 

525 

580 

462 

504 

46o 

19-4 

33-5 

18.3 

10.8 

9-2 

8.2 

26.2 

34-0 

30.6 

97-7 

98.2 

98.2 

99-8 

97.5 

97.3 

98.2 

96.2 

98.8 

o.o 

0.7 

1.7 

O.  2 

0.4 

2.O 

0.8 

3.8 

0.5 

0.3 

0.35 

0.8 

1.4 

0.3 

0-5 

1.2 

1.3 

i.i 

O.I 

0.4 

i.i 

0.0 

o.o 

O.2 

2.1 

4-3 

o.o 

94-6 

88  3 

95-2 

IOO.O 

92.1 

96.4 

92.O 

82.2 

99-0 

o  o 

o.o 

O  O 

0.0 

4Q 

0.0 

O.I 

a  o 

o.o 
o.o 

o.o 

O.O 
O.S 

0.2 
1.2 

0.3 

0.0 

,o 

60  5 

46.5 

*3-4 

36.5 

39*5 

103.5 

95.4 

92.9 

53.9 

88.7 

59-7 

106.0 

120.4 

155.9 

151.0 

172.0 

139-4 

67.3 

125.2 

98,0 

97.o 

7.0 

2,0 

4.6 

2-7 

6.0 

75-0 

60.6 

O2     fi 

GT   *i 

QO   < 

Qsj  o 

96.0 

90.0 

93  .0 

fi    A 

yi  .  y 
8  * 

9t 

S-o 

4.0 

10,0 

O.4 

0.55 

0,8 

2-35 

406          FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH      XIX 

Only  cyclic  bodies  containing  sulfur  in  ring  formation  give  precipi- 
tates with  mercury. 

E.  Donath  and  B.  M,  Margosches2*  state  that  wool-grease 
pitch  may  be  identified  by  boiling  10  g.  of  the  material  with  50  cc. 
N— 2  alcoholic  potash  under  a  reflux  condenser  for  ^  hour,  and 
then  filtering  the  hot  liquid.  A  precipitate  will  form  in  the  filtrate 
on  cooling,  consisting  of  the  potassium  salts  of  hydroxy  fatty  acids, 
which  upon  recrystallizing  from  boiling  95  per  cent  alcohol  and 
transposing  with  hydrochloric  acid,  will  form  a  white  crystalline 
mass  of  the  hydroxy  fatty  acids  melting  at  80-82°  C.,  which  is  in- 
soluble in  water  and  soluble  in  hot  naphtha.  It  is  claimed  that  by 
this  method  25  per  cent  of  wool-grease  pitch  may  be  detected  in 
admixture  with  other  pitches.  A  further  means  of  identification 
depends  upon  the  fact  that  wool-fat  pitches  give  the  cholesterol 
reaction. 

The  author  has  found  the  lineal  coefficient  of  expansion  of  fatty- 
acid  pitches  for  i°  F.  (length  =  i)  to  average  0.00023. 

Fatty-acid  pitches  flux  satisfactorily  with  mineral  waxes,  native 
and  pyrogenous  asphalts,  tars  and  pitches.  They  also  flux  satisfac- 
torily with  gilsonite  and  glance  pitch,  but  not  with  grahamite* 

The  following  figures  indicate  that  the  hardening  (toughening) 
of  fatty-acid  pitches  on  exposure  to  the  weather  is  due  to  oxidation. 
A  sample  of  soft  fatty-acid  pitch  (the  first  in  Table  XXVIII)  was 
melted  and  poured  into  a  shallow  glass  dish,  forming  a  layer 
exactly  I  millimeter  thick.  This  was  exposed  out  of  doors  for  one 
year  in  a  dust-free  receptacle,  protected  from  the  direct  action  of 
the  weather,  and  the  following  increases  in  weight  noted : 

After  i  month  gained  0.62  per  cent         After  7  months  gained  4.20  per  cent 

2  months  2 . 52  per  cent  8  4 . 27  per  cent 

3  3.27  per  cent  9  4.30  per  cent 

4  3. 50  per  cent  10  4.38  per  cent 

5  3. 86  per  cent  n  4.42  per  cent 

6  4.12  per  cent  12  4.46  per  cent 

The  original  pitch  was  soft  and  semi-liquid,  but  after  exposure 
for  one  year  it  hardened  to  a  tough,  leathery  mass.  The  original 
fusing-point  was  44^°  F.  (K.  and  S.  method),  and  at  the  end  of 
the  year  it  was  185°  F. 


XIX  BONE  TAR  AND  BONE-TAR  PITCH  407 


BONE  TAR  AND  BONE-TAR  PITCH 

In  the  production  of  bone  tar  and  bone-tar  pitch  the  crude  bones 
are  first  steeped  in  a  i  per  cent  solution  of  brine  for  three  to  four 
days,  to  separate  the  fibrous  matter.  They  are  then  degreased  by 
one  of  the  following  methods : 

(1)  Boiling  the  bones  with  water  in  open  vessels; 

(2)  Boiling  with  water  in  closed  tanks  under  a  pressure  of 
10  ib.; 

(3)  Extracting  the  bones  with  a  solvent  (usually  a  petroleum 
distillate  boiling  at  100°  C.)  and  removing  the  last  traces  of  solvent 
from  the  bones  by  blowing  in  live  steam.    The  degreased  bones  are 
then  treated  to  extract  the  glue  by  again  subjecting  the  bones  to  the 
action  of  live  steam  for  a  lengthy  period  under  a  pressure  of  I  C  to 
20  Ib.  in  an  upright  cylindrical  boiler  with  a  false  bottom.     The 
glue  gradually  leaches  from  the  bones,  the  quantity  extracted  de- 
pending upon  the  duration  of  the  treatment.     When  it  is  desired 
to  convert  the  bones  into  "bone  charcoal"  (used  for  the  purification 
of  petroleum  distillates  and  paraffin  wax),  only  one-half  of  the 
gelatinous  matter  is  extracted  from  the  degreased  bones,  whereupon 
the  water  is  drained  off  and  the  bones  allowed  to  air-dry.     They 
are  then  distilled  destructively  in  horizontal  cast-iron  retorts,  the 
distillate  being  condensed,  and  the  permanent  gases  consumed  under 
the  retort.     The  distillate  consists  of  an  alkaline  aqueous  liquor 
containing  ammoniacal  bodies,  and  1.5-2.0  per  cent  (based  on  the 
weight  of  raw  material  used)  of  a  tarry  layer  known  as  "bone  tar," 
"bone  oil,"  "Dippel  oil,"  or  "Oleum  animale  foetidum."    The  resi- 
due remaining  in  the  retort,  known  as  "bone  charcoal"  or  "animal 
charcoal,"  is  removed  while  still  hot,  and  transferred  to  an  air-tight 
vessel  in  which  it  is  allowed  to  cool.     It  is  then  passed  through 
grinding  mills  and  sieved.    The  bone  charcoal  is  composed  of  ap- 
proximately 10  per  cent  of  carbon,  75  per  cent  of  calcium  phos- 
phate, the  balance  consisting  of  various  other  mineral  ingredients 
and  moisture. 

The  following  yields  are  obtained : 

Non-condensable  gases 10-15  per  cent 

Aqueous  liquor 10-15  per  cent 

Bone  tar 25-10  per  cent 

Bone  charcoal 55~6o  per  cent 

Total loo-ioo  per  cent 

The  bone  tar  floating  on  the  surface  of  the  aqueous  liquor  is 
drawn  off.  It  consists  of  fatty  substances  derived  from  the  fat 


408          FATTY-ACID  PITCH,  BONE  TAR  AND  BONE-TAR  PITCH       XIX 

which  escaped  extraction  from  the  bones,  also  derivatives  of  pyri- 
dine  possessing  a  most  disagreeable  and  penetrating  odor,  and  inci- 
dentally serving  to  distinguish  it  from  all  other  tars.  The  charac- 
teristics of  bone  tar  are  included  in  Table  LXXXIV. 

The  aqueous  liquor  is  distilled,  and  the  distillate  caught  in  sul- 
furic  acid  to  recover  the  ammonium  compounds  as  ammonium  sul- 
fate.  The  residue  is  used  as  a  fertilizer. 

The  bone  tar  is  subjected  to  fractional  distillation  to  recover  the 
bone-tar  pitch,  the  properties  of  which  are  also  embodied  in 
Table  LXXXIV. 

Bone-tar  pitch  is  intermediate  in  its  physical  properties  between 
asphalts  and  the  fatty-acid  pitches.  On  destructive  distillation,  it 
yields  an  aqueous  distillate  which  reacts  distinctly  alkaline.  It  is 
moderately  susceptible  to  temperature  changes,  and  on  a  par  with 
higher  grades  of  residual  asphalts  and  inferior  grades  of  fatty-acid 
pitches  in  its  weather-resisting  properties.  It  is  the  blackest  of  all 
pitches  and  is  therefore  valued  by  the  varnish  maker  to  deepen  the 
color  of  japans.  It  is  soluble  in  pyridine  bases  and  only  partly 
soluble  in  benzol  and  petroleum  distillates,  but  upon  fluxing  with 
rosin  and  vegetable  oils  it  becomes  soluble.  Since  it  is  produced  in 
comparatively  small  quantities,  it  can  scarcely  be  regarded  as  a 
commercial  product 

GLYCERIN  PITCH 

This  pitch  is  obtained  upon  the  purification  of  glycerin  by  dis- 
tillation with  superheated  steam.  It  is  greenish  brown  to  black  in 
color  and  contains  a  certain  amount  of  water-soluble  constituents. 
It  is  produced  in  limited  quantities  and  has  a  restricted  use.27 

Glycerin  pitch  contains  polyglycerins,  metallic  soaps,  metallic 
salts,  etc.  It  is  used  as  a  lubricant  in  boring,  for  making  printing 
inks,  as  a  core  binder,28  etc.  Upon  heating  with  phthalic  anhydride 
and  succinic,  malic,  fumaric,  citric,  or  malomalic  acid,  a  water- 
resistant  synthetic  resin  is  obtained.29 


PART  IF 
PYROGENOUS  ASPHALTS  AND  WAXES 

CHAPTER  XX 
PETROLEUM  ASPHALTS 

"Petroleum  asphalts"  are  obtained  from  petroleums  by  distilla- 
tion, blowing  with  air  at  elevated  temperatures,  and  in  the  refining 
of  certain  distillates  with  sulfuric  acid.  These  methods  will  be 
described  in  greater  detail  later. 

Varieties  of  Petroleum.  Petroleum  as  it  occurs  in  different 
parts  of  the  world,  varies  widely  in  composition.  Certain  varieties 
are  composed  of  open  chain  hydrocarbons,  others  are  made  up 
exclusively  of  cyclic  hydrocarbons,  and  still  others  occur  showing 
every  possible  gradation  between  these  two  extremes.  Numerous 
classifications  have  been  proposed,  based  on  its  chemical  composi- 
tion in  general,  or  the  presence  of  a  substantial  proportion  of  char- 
acteristic bodies,  such  as  the  paraffin  series  of  hydrocarbons,  the 
naphthene  series,  sulfur  derivatives,  nitrogenous  bodies,  benzols, 
terpenes,  etc.1 

From  the  standpoint  of  the  asphalt  content,  petroleums  may  be 
divided  into  three  groups,  viz. : 

(1)  Asphaltic  petroleums.    These  carry  a  substantial  amount 
of  asphaltic  bodies,  with  solid  paraffins  either  absent  or  present  only 
in  traces. 

(2)  Semi-asphaltic    petroleums.      These    carry    a    moderate 
amount  of  asphaltic  bodies,  but  in  any  event  generate  or  produce 
asphalt-like  bodies  during  the  distillation  process.     Solid  paraffins 
may  or  may  not  be  present 

(3)  Non-asphaltic  petroleums.    These  do  not  carry  asphaltic 
bodies  but  may  generate  them  during  the  distillation  process.    Solid 
paraffins  are  usually  present,  but  not  necessarily  so. 

409 


410 


PETROLEUM  ASPHALTS 


XX 


XX 


DEHYDRATION  OF  PETROLEUM 


411 


Table  XXIX  contains  a  list  of  the  most  important  occurrences 
of  petroleum  throughout  the  world,  classified  according  to  the  as- 
phalt content  and  solid  paraffins  present. 

Different  crudes  yield  varying  amounts  of  asphalt  on  steam  or 
vacuum  distillation,  dependent  upon  the  character  of  the  oil  and  the 
amount  of  asphalt  content  The  following  figures  are  illustrative, 
and  indicate  in  a  general  way  the  yield  of  asphalt  by  weight,  having 
a  fusing-point  of  100°  F.  (R.  and  B.  method)  : 


Type  of  Crude  Oil 

A.  P.  I.  Gravity 

Yield  of  Asphalt 

Mid-continental  (Oklahoma)  

42° 

2  per  cent 

Seminole  

36° 

ik  oer  cent 

Peruvian  

36° 

4  per  cent 

Mid-continental  (Illinois)  

32° 

5J  per  cent 

Light  Californian  

26° 

12  per  cent 

Texan.  

24° 

14  per  cent 

Heavy  Californian.  

12° 

65  per  cent 

Mexican  (Panuco)  

12° 

65  per  cent 

DEHYDRATION  OF  PETROLEUM 

Nearly  all  crude  petroleums  carry  more  or  less  water,  some 
being  entrained  mechanically,  and  in  other  cases  held  in  a  state  of 
emulsion.  Ordinarily  the  oil  is  permitted  to  stand  long  enough  by 
itself  for  the  water  and  sand  to  separate.  Crude  oils  containing 
less  than  2  per  cent  of  water  are  accepted  by  the  pipe  lines  and  re- 
fineries. If  they  contain  more  than  2  per  cent,  they  must  first  be 
dehydrated.  Certain  heavy  asphaltic  and  waxy  crudes  carry  as 
much  as  70  to  90  per  cent  of  water  held  in  suspension  by  brine  and 
colloidal  mineral  matter  (e.  g.,  hydrated  aluminium  silicates).  The 
following  methods  may  be  used  to  remove  the  water,  where  it  is 
necessary  to  deliver  the  oil  to  the  pipe  line  or  refinery  within  the 
prescribed  limitations : 

1 i )  Settling.    Heating  and  subsidence  will  break  up  emulsions 
in  many  cases.    This  may  be  facilitated  by  adding  chemicals,  as  for 
example  i  per  cent  of  a  mixture  of  sodium  oleate,  sodium  resinate 
and  sodium  silicate ;  or  else  sulf onated  pleic  acid.2 

(2)  Centrifugtng.     This  consists  in  centrifuging  the  oil  at  a 
temperature  of  no  to  180°  F.  in  a  centrifuge  operating  at  17,000 
r.p.m.  by  means  of  a  turbine.3 


412  PETROLEUM  ASPHALTS  XX 

(3)  Tube  Stills.  The  most  satisfactory  manner  to  break  up 
emulsions  consists  in  running  the  oil  through  a  tube-  or  pipe-still 
under  pressure  and  heated  to  300°  F.,  whereupon  it  is  released  in 
a  vaporizer  at  atmospheric  pressure.  The  water  and  oil  vapors 
are  recondensed,  but  will  not  again  emulsify  on  account  of  the  ab- 
sence of  emulsifying  agents  and  the  low  viscosity  of  the  oil. 

DISTILLATION  OF  PETROLEUM 

Petroleum  is  separated  into  various  commercial  products  by 
means  of  distillation,  of  which  the  following  methods  are  in  vogue : 

(i)  Batch  Stills.  These  are  still  in  use  in  the  older  refineries, 
but  are  rapidly  being  superseded  by  tube  stills.  The  efficiency  in 
transmission  of  heat  to  the  oil  in  the  batch  still  is  very  poor,  being 
rarely  better  than  30  per  cent,  equivalent  to  a  consumption  of  6 
bbl.  of  fuel  oil  for  each  100  bbl.  of  distillate.  Approximately  0.85 
bbl.  distillate  is  produced  per  day,  per  sq.  ft.  of  surface  fired,  or 
expressed  differently,  2.5  gal.  distillate  will  vaporize  per  hour,  per 
sq.  ft.  vaporizing  surface.  Fig.  121  illustrates  a  typical  batch-still 
installation.  The  still  proper  holds  1000  to  1500  bbl.  of  42  gal", 
each.  The  distillation  process  may  be  carried  on  either  with,4  or 
without  the  use  of  steam.  Where  steam  is  employed,  the  process 
is  known  as  "steam  distillation,"  otherwise  it  is  termed  "dry  dis- 
tillation." 

Steam  Distillation.  This  is  also  known  as  the  "fractional"  dis- 
tillation process  and  consists  in  introducing  dry  steam,  termed  "bot- 
tom steam"  into  the  still,  which  assists  in  the  vaporization  of  the 
volatile  constituents  and  minimizes  decomposition  of  the  distillate 
and  residue.  Its  action  is  based  on  the  physical  law  that  the  boiling- 
point  of  a  pair  of  non-miscible  or  slightly  miscible  liquids  is  lower 
than  that  of  either  pure  component.  The  introduction  of  steam, 
therefore,  serves  materially  to  lower  the  boiling-point  of  the  petro- 
leum, and  produces  the  maximum  yield  of  heavy  lubricating  oils. 
It  also  tends  to  economize  in  fuel,  and  to  shorten  the  distillation 
process.  The  steam  upon  being  dried  by  passing  through  a  trap  is 
introduced  through  perforated  pipes  at  the  bottom  of  the  still  when 
the  temperature  of  the  contents  exceeds  the  boiling-point  of  water. 

In  treating ^asphaltic  petroleums  by  the  steam-distillation  proc- 
ess in  batch  stills,  the  charge  is  distilled  until  the  residue  attains 
the  proper  consistency,  which  is  controlled  by  sampling  the  residue 
through  petcocks  set  in  the  still,  or  by  recording  the  temperature  of 
the  residue,  or  by  observing  the  character  of  the  distillate.  The 
further  the  process  is  continued,  the  higher  will  be  the  fusing-point 
and  the  harder  the  consistency  of  the  residue.  The  temperature  of 
the  residue  at  the  termination  of  the  process  will  vary  between  600 


XX 


DISTILLATION  OF  PETROLEUM 


413 


and  750°  F.,  and  the  time  of  distillation  between  twelve  and  thirty- 
six  hours.  When  the  distillation  is  completed,  the  residuum  is  run 
or  blown  into  a  closed  cylindrical  vessel  constructed  of  steel,  where 


it  is  allowed  to  cool  until  the  temperature  is  reduced  sufficiently  to 
permit  its  being  filled  into  barrels  or  drums  without  danger  of  ig- 
niting on  coming  in  contact  with  air. 


414  PETROLEUM  ASPHALTS  XX 

Where  the  residue  is  distilled  to  a  definite  consistency  without 
further  treatment,  the  distillation  is  known  as  Straight  running, 
and  the  residue  a  "straight  run  asphalt."  In  certain  cases  a  portion 
or  "fraction"  of  the  distillate  is  mixed  with  the  residue  at  the  close 
of  the  distillation,  which  is  termed  "cutting  back,"  5  the  object  of 
which  is  to  modify  the  properties  of  the  residual  product  or  to 
dispose  economically  of  a  fraction  which  otherwise  has  little  value 
commercially. 

Cut-back  residual  oil  is  composed  of  residual  oil,  cut  back  with 
a  petroleum  distillate,  which  should  be  of  a  character  which  will 
volatilize  within  a  reasonably  short  time  after  application  to  a  sur- 
face. Relatively  volatile  distillates  are  generally  used  in  the  manu- 
facture of  cut-back  asphalts.  The  larger  the  quantity  of  distillate 
added,  the  more  fluid  will  be  the  cut-back  product.6 

In  treating  semi-asphaltic  and  non-asphaltic  petroleums  by  the 
steam-distillation  process  in  batch  stills,  steam  is  introduced  when 
all  the  naphtha  has  distilled  off,  and  the  distillation  continued  until 
the  lubricating  oils  have  distilled  over,  whereupon  the  temperature 
reaches  620°  F.  At  this  point  the  distillation  is  stopped.  In  the 
case  of  non-asphaltic  crude  oil,  the  so-called  "cylinder  stock"  re- 
mains in  the  still,  and  with  semi-asphaltic  crude,  an  asphaltic  residue 
remains  behind,  which  may  either  be  marketed  as  such,  or  treated 
with  air  to  produce  a  "blown  asphalt." 

Table  XXX  gives  an  outline  of  the  steam-distillation  process  as 
applied  to  asphaltic  petroleum,  and  Table  XXXI  as  applied  to 
semi-asphaltic  and  non-asphaltic  petroleums.  ^ 

Dry  Distillation.  This  is  sometimes  termed  the  straight  or 
"destructive"  or  "cracking"  distillation,  by  means  of  which  a  certain 
proportion  of  the  higher  boiling-point  constituents  decompose  or 
break  down,  forming  correspondingly  larger  yields  of  the  low  boil- 
ing-point constituents.  The  dry  distillation  process  is  accordingly 
used  when  the  distiller  wishes  to  produce  a  maximum  amount  of 
gasoline  and  illuminating  oil,  or  in  cases  where  the  crude  is  unfit 
for  manufacturing  lubricating  oil. 

Upon  treating  semi-asphaltic  and  non-asphaltic  petroleums  by 
the  dry-distillation  process  in  batch  stills,  a  large  amount  of  crack- 
ing taices  place  when  the  crude  kerosene  fraction  distils  over  and 
the  temperature  of  the  still  reaches  625°  F.  The  fires  are  accord- 
ingly moderated  to  slow  down  the  distillation  and  accelerate  the 
decomposition  as  much  as  possible.  The  "cracked"  distillate  is 
fractioned  until  the  temperature  in  the  still  reaches  675  to  700°  F., 
whereupon  the  distillation  is  brought  to  a  close.  There  remains  a 
viscous  dark-colored  "residuum"  varying  in  gravity  from  20  to  25° 
Baume  which  may  either  be  marketed  under  the  name  of  "residual 
oil"  or  "flux  oil"  or  else  distilled  separately  in  another  still,  known 


XX 


DISTILLATION  OF  PETROLEUM 


415 


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PETROLEUM  ASPHALTS 


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XX  DISTILLATION  OF  PETROLEUM  417 

as  a  "tar  still,"  to  obtain  the  wax  or  paraffin  distillate,  wax-tailings 
and  coke  bottoms.  The  operation  is  carried  on  as  rapidly  as  pos- 
sible to  avoid  unnecessary  cracking,  and  render  the  paraffin  crystal- 
line* The  paraffin  distillate  comes  over  first,  followed  by  the  wax- 
tailings,  until  nothing  but  the  coke  remains  in  the  still,  which  after 
cooling  is  removed  with  a  pick  and  shovel.  The  method  of  pro- 
cedure is  illustrated  in  Table  XXXII. 

(2)  Continuous  Stills.    Stills  of  this  type  are  now  encountered 
infrequently.     They  are  constructed  similar  to  batch  stills,  the  oil 
flowing  from  one  still  to  another,  and  each  producing  a  predeter- 
mined grade  of  distillate.    The  whole  circumference  of  a  continuous 
still  may  be  fired  and  approximately  1.42  bbl.  of  distillate  will  be 
obtained  per  day,  per  square  foot  of  firing  surface,  similarly  2.5  gal. 
of  distillate  will  evaporate  per  square  foot  of  vaporizing  surface. 
The  efficiency  of  continuous  stills  is  approximately  40  per  cent, 
equivalent  to  a  consumption  of  5  bbl.  of  fuel  oil  per  100  bbl.  dis- 
tillate produced. 

(3)  Tube  or  Pipe  Stills.    Tube  or  pipe  stills,  aiso  termed  'Vac- 
uum  flash  coils"   when   connected  with  vacuum   fractioning    (or 
"flash")  chambers7  are  rapidly  replacing  the  other  types  of  stills 
on  account  of  their  lower  initial  cost,  greater  through-put,  and  econ- 
omy in  operation.     The  oil  is  pumped  under  pressure  through  a 
series  of  interconnecting  tubes  heated  in  a  furnace.     Such  stills  are 
built  in  units  capable  of  handling  up  to  15,000  bbl.  of  crude  oil  per 
day.    It  is  possible  to  heat  the  oil  as  high  as  900  to  950°  F.  because 
of  the  high  rate  of  heat  transfer  through  the  tubes  and  the4iigh 
velocity  of  the  oil.     This  heat  transfer  may  run  as  high  as  200 
B.t.u.  per  sq.  ft.,  per  hour,  per  degree  F.  difference  in  temperature. 
Their  efficiency  will  range  from  65  to  80  per  cent,  equivalent  to  a 
consumption  of  less  than  3  bbl.  fuel  oil  per   100  bbl.  distillate 
produced. 

By  means  of  a  tube  still,  as  much  as  90  per  cent  of  the  crude 
may  be  recovered  as  distillate  and  it  is  not  infrequent  that  10  per 
cent  more  gasoline  will  be  obtained  than  is  present  in  the  crude  oil 
under  treatment,  due  to  the  cracking  which  takes  place.  Wh